Process for Producing Aromatic Carbonate

ABSTRACT

Production of an aromatic carbonic ester through an ester exchange reaction between a starting material and a reactant while distilling by-product alcohols and/or by-product dialkyl carbonates off the reaction system, wherein use is made of a specified catalyst.

TECHNICAL FIELD

The present invention relates to a method for producing an aromatic carbonate. More specifically, the present invention relates to a method capable of producing a high purity aromatic carbonate in a stable manner for a long period, which comprises allowing to react a starting material selected from the group consisting of a dialkyl carbonate, an alkylaryl carbonate and a mixture thereof and a reactant selected from the group consisting of an aromatic monohydroxy compound, an alkylaryl carbonate and a mixture thereof in the presence of a metal-containing catalyst which has a molecular weight of 450 or more and which is in the form of liquid or dissolved in a liquid phase in the reaction system, with distilling off by-product alcohol and/or by-product dialkyl carbonate to the outside of the reaction system.

BACKGROUND ART

Aromatic carbonate is useful as a raw material for producing aromatic polycarbonate which is recently becoming more and more important as an engineering plastic, without using poisonous phosgene, or as a raw material for producing isocyanate without using poisonous phosgene. Referring to the method of producing an aromatic carbonate, a method is known, which comprises subjecting dialkyl carbonate, alkylaryl carbonate or a mixture thereof which is a starting material and an aromatic monohydroxy compound, an alkylaryl carbonate or a mixture thereof which is a reactant to an transesterification to produce a corresponding aromatic carbonate or an aromatic carbonate mixture.

However, all such transesterification are an equilibrium reaction, and due to the reactant-favored equilibrium and its low reaction rate, industrial production of aromatic carbonate by this method has been very difficult. Several approaches have been proposed in order to make this method improvements, and most of them relate to catalysts for increasing the reaction rate and a number of metal-containing catalysts are known. In a method for producing alkylaryl carbonate, diaryl carbonate or a mixture thereof by a reaction between dialkyl carbonate and an aromatic hydroxy compound, the following catalysts are proposed as such catalysts: Lewis acid such as transition metal halide or a compound which produces Lewis acid (Patent Document 1, Patent Document 2, Patent Document 3 (which is corresponding to Patent Documents 4 to 6)), tin compounds such as organic tin alkoxide and organic tin oxide (Patent Document 7 (which is corresponding to Patent Document 8)), Patent Document 9, Patent Document 10 (which is corresponding to Patent Document 11), Patent Document 12 (which is corresponding to Patent Document 13), Patent Document 14, and Patent Document 15), salts and alkoxides of alkali metal or alkaline earth metal (Patent Document 16), lead compounds (Patent Document 16), complexes of metal such as copper, iron or zirconium (Patent Document 17), titanates (Patent Document 18 which is corresponding to Patent Document 19), a mixture of Lewis acid and protonic acid (Patent Document 20 which is corresponding to Patent Document 21), a compound of Sc, Mo, Mn, Bi, Te (Patent Document 22) and ferric acetate (Patent Document 23).

In addition, in a method of producing diaryl carbonate by disproportionation of diaryl carbonate and diaryl carbonate by an transesterification between the same kind of molecules of alkylaryl carbonate, the following catalysts are proposed as such catalysts: Lewis acid and a transition metal compound which can produce Lewis acid (Patent Document 24 which is corresponding to Patent Documents 25 and 26), a polymeric tin compound (Patent Document 27 which is corresponding to Patent Document 28), a compound represented by the formula R—X(═O)OH (in which X is selected form Sn and Ti and R is selected from monovalent hydrocarbon groups) (Patent Document 29 which is corresponding to Patent Document 30), a mixture of Lewis acid and protonic acid (Patent Document 31 which is corresponding to Patent Document 32), a lead catalyst (Patent Document 33), a titanium or zirconium compound (Patent Document 34), a tin compound (Patent Document 35) and a compound of Sc, Mo, Mn, Bi, Te (Patent Document 36).

On the other hand, it is also attempted to improve the yield of aromatic carbonate by shifting the equilibrium to the product side as much as possible by designing a suitable reaction system. For example, a method in which by-product methanol is distilled off together with an azeotropic agent by azeotropic distillation in a reaction between dimethyl carbonate and phenol (Patent Document 37 and corresponding Patent Documents 38 and 39, Patent Document 40) and a method in which by-product methanol is removed by adsorption using molecular sieve (Patent Document 41 which is corresponding to Patent Document 42) are proposed.

Further, a method in which alcohol produced by the above-mentioned reaction is distilled off from a reaction mixture using an apparatus having a distillation column on the upper part of a reactor is also known (Examples of Patent Document 43 which is corresponding to Patent Document 44, Examples of Patent Document 45, Examples of Patent Document 46 and corresponding Patent Document 47, Examples of Patent Document 48 which is corresponding Patent Document 49, Examples of Patent Document 50 which is corresponding Patent Document 51), Examples of Patent Documents 52, 53 and 54). carbonate by these methods, methods for stable and long-term operation have also been proposed. Patent Document 64 discloses a method in which aliphatic alcohol is removed from a distillation column connected to a reactor so that the concentration of the aliphatic alcohol in the reactor is 2% by weight or less upon production of aromatic carbonate from dialkyl carbonate and an aromatic hydroxy compound, and it is described that stable continuous operation was achieved. The method of the publication is directed to avoid problems of precipitation of catalyst in the distillation column. Further, Patent Document 65 discloses a method which enables long-term stable operation by suppressing precipitation of catalyst by controlling the weight ratio of an aromatic polyhydroxy compound and/or a residue thereof to 2 or less relative to the metal component of the catalyst in a liquid matter in the system containing the catalyst.

On the other hand, the catalyst used in this reaction system is usually dissolved in a reaction mixture under reaction conditions, and has a higher boiling point than aromatic carbonate. Therefore, to obtain high purity aromatic carbonate from the reaction mixture, low boiling point components are first removed from the mixture and then diaryl carbonate of the high boiling point components is separated from the catalyst so as to purify the diaryl carbonate. It is known that the catalyst may be recovered and reused as a high boiling point component in that case, and deactivated components may be removed. Examples of such method of separating catalyst are described in Patent Document 66.

Titanium compounds are known to be an excellent catalyst (e.g., Patent Documents 67 and 68). However, when titanium based catalysts, for example, titanium phenoxide: Ti(OPh)₄ or titanium alkoxide: Ti(OR)₄, is used, there is a problem that diaryl carbonate which is the final product is colored with dark red as described in Patent Document 69. This is because, since titanium butoxide: Ti(OBu)₄ typically used has a boiling point of 206° C. at 1.3 KPa and titanium phenoxide typically used has a boiling point of about 250° C. at about 27 Pa (No patent Document 1), they are also distilled off in a proportion corresponding to their vapor pressure upon separation of diaryl carbonate by distillation and therefore not sufficiently separated from the product. Further, as described in Patent Document 70, degradation of catalyst and deterioration of diaryl carbonate due to high temperature in separation of titanium phenoxide have been reported. Also, Patent Document 71 describes a problem that when Ti(OPh)₄ is used and a mixture of starting materials and a catalyst is supplied to a continuous multi-stage distillation column to continue the reaction, the distillation column may be clogged. Thus, the well-known titanium based catalysts have problems that due to their high vapor pressure under reaction conditions, separation of produced diaryl carbonate is difficult, and the fraction at high temperature for a long period causes degradation of catalyst, clogging of the distillation column and deterioration of diaryl carbonate.

[Patent Document 1] JP-A-51-105032

[Patent Document 2] JP-A-56-123948

[Patent Document 3] JP-A-56-123949

[Patent Document 4] DE 2528412

[Patent Document 5] GB Patent No. 1499530

[Patent Document 6] U.S. Pat. No. 4,182,726

[Patent Document 7] JP-A-54-48733

[Patent Document 8] DE 2736062

[Patent Document 9] JP-A-54-63023

[Patent Document 10] JP-A-60-169444

[Patent Document 11] U.S. Pat. No. 4,554,110

[Patent Document 12] JP-A-60-169445

[Patent Document 13] U.S. Pat. No. 4,552,704

[Patent Document 14] JP-A-62-277345

[Patent Document 15] JP-A-1-265063

[Patent Document 16] JP-A-57-176932

[Patent Document 17] JP-A-57-183745

[Patent Document 18] JP-A-58-185536

[Patent Document 19] U.S. Pat. No. 4,410,464

[Patent Document 20] JP-A-60-173016

[Patent Document 21] U.S. Pat. No. 4,609,501

[Patent Document 22] JP-A-1-265064

[Patent Document 23] JP-A-61-172852

[Patent Document 24] JP-A-51-75044

[Patent Document 25] DE 2552907

[Patent Document 26] U.S. Pat. No. 4,045,464

[Patent Document 27] JP-A-60-169444

[Patent Document 28] U.S. Pat. No. 4,554,110

[Patent Document 29] JP-A-60-169445

[Patent Document 30] U.S. Pat. No. 4,552,704

[Patent Document 31] JP-A-60-173016

[Patent Document 32] U.S. Pat. No. 4,609,501

[Patent Document 33] JP-A-1-93560

[Patent Document 34] Japanese Patent No. 2540590

[Patent Document 35] JP-A-1-265063

[Patent Document 36] JP-A-1-265064

[Patent Document 37] JP-A-54-48732

[Patent Document 38] DE 736063

[Patent Document 39] U.S. Pat. No. 4,252,737

[Patent Document 40] JP-A-61-291545

[Patent Document 41] JP-A-58-185536

[Patent Document 42] U.S. Pat. No. 4,104,64

[Patent Document 43] JP-A-56-123948

[Patent Document 44] U.S. Pat. No. 4,182,726

[Patent Document 45] JP-A-56-25138

[Patent Document 46] JP-A-60-169444

[Patent Document 47] U.S. Pat. No. 4,554,110

[Patent Document 48] JP-A-60-169445

[Patent Document 49] U.S. Pat. No. 4,552,704

[Patent Document 50] JP-A-60-173016

[Patent Document 51] U.S. Pat. No. 4,609,501

[Patent Document 52] Examples of JP-A-61-172852

[Patent Document 53] Examples of JP-A-61-291545

[Patent Document 54] JP-A-62-277345

[Patent Document 55] JP-A-3-291257

[Patent Document 56] JP-A-4-9358

[Patent Document 57] JP-A-6-41022

[Patent Document 58] JP-A-6-157424

[Patent Document 59] JP-A-6-184058

[Patent Document 60] JP-A-6-234707

[Patent Document 61] JP-A-6-263694

[Patent Document 62] JP-A-6-298700

[Patent Document 63] JP-A-6-345697

[Patent Document 64] JP-A-6-157410

[Patent Document 65] National Publication of International Patent Application No. 9-11049

[Patent Document 66] JP-A-9-169704

[Patent Document 67] DE Patent No. 2,528,412

[Patent Document 68] DE Patent No. 2,552,907

[Patent Document 69] EP Patent No. 879

[Patent Document 70] JP-A-9-169704

[Patent Document 71] JP-A-2004-307400

[Non-patent Document 1] J. Inorg. Nucl. Chem. Vol. 28, 2410 (1966)

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention

An object of the present invention is to provide a method of producing high purity diaryl carbonate in which a catalyst can be easily separated without the above-described problems, when producing an aromatic carbonate by allowing to react a starting material selected from the group consisting of a dialkyl carbonate, an alkylaryl carbonate and a mixture thereof and a reactant selected from the group consisting of an aromatic monohydroxy compound, an alkylaryl carbonate and a mixture thereof in the presence of a metal-containing catalyst, with distilling off by-product alcohol and/or by-product dialkyl carbonate to the outside of the reaction system.

Means for Solving the Problems

As a result of intensive studies conducted by the present inventors to solve the aforementioned problems, the inventors have found that the object can be achieved by using a specific metal-containing catalyst as a catalyst when producing an aromatic carbonate by allowing to react a starting material selected from the group consisting of a dialkyl carbonate, an alkylaryl carbonate and a mixture thereof with a reactant selected from the group consisting of an aromatic monohydroxy compound, an alkylaryl carbonate and a mixture thereof in the presence of a metal-containing catalyst, with distilling off by-product alcohol and/or by-product dialkyl carbonate to the outside of the reaction system, and the present invention has been completed. Surprisingly, the present invention can solve the problem of conventional method that clogging and blocking of distillation column frequently occur when reactants and a catalyst are supplied to the middle plate of the distillation column, and the present invention also makes it easier to separate produced diaryl carbonate from other components and thus can produce high purity diaryl carbonate in which the amount mixed of a metal compound derived from a catalyst is extremely small.

Accordingly, the present invention is as follows.

[1] A method for producing an aromatic carbonate, which comprises allowing to react a starting material selected from the group consisting of a dialkyl carbonate represented by the following formula (1), an alkylaryl carbonate represented by the following formula (2) and a mixture thereof with a reactant selected from the group consisting of an aromatic monohydroxy compound represented by the following formula (3), an alkylaryl carbonate represented by the following formula (4) and a mixture thereof in the presence of a metal-containing catalyst, with distilling off by-product alcohols and/or by-product dialkyl carbonates to the outside of the reaction system, thereby producing an aromatic carbonate represented by the following formula (5) and/or the following formula (6) corresponding to the starting material and the reactant, wherein the metal-containing catalyst has a molecular weight of 450 or more and is dissolved in a liquid phase in the reaction system or present in the form of liquid during the reaction,

(wherein R¹, R² and R³ in the formulas (1) to (4) independently represent an alkyl group having 1 to 10 carbon atoms, an alicyclic group having 3 to 10 carbon atoms or an aralkyl group having 6 to 10 carbon atoms, and Ar¹, Ar² and Ar³ independently represent an aromatic group having 5 to 30 carbon atoms), and

(wherein R and Ar in the formulas (5) and (6) are each selected from R¹, R², R³, Ar¹, Ar² and Ar³ of the corresponding starting material and reactant).

[2] The method according to [1], wherein the metal-containing catalyst is a molecular weight of 480 or more.

[3] The method according to [1], wherein the metal-containing catalyst is a titanium containing compound.

[4] The method according to [3], wherein the titanium containing compound is an organic polytitanoxane composition.

[5] The method according to [4], wherein the organic polytitanoxane composition contains at least one alkoxy group and/or aryloxy group as an organic group.

[6] The method according to [4], wherein the organic polytitanoxane composition is obtained by a polycondensation reaction of at least one raw material selected from the group consisting of tetraalkoxytitanium, tetrahalotitanium (TiX₄:X being selected from Cl and Br) and titanium hydroxide.

[7] The method according to [6], wherein the organic polytitanoxane composition is obtained by sequentially or simultaneously performing the two steps of:

1) preparing a partially hydrolyzed product by partially hydrolyzing tetraalkoxytitanium and

2) distilling off a generated low boiling point component including alcohol from the partially hydrolyzed product and subjecting the product to polycondensation.

[8] The method according to [6], wherein the organic polytitanoxane composition is obtained by subjecting tetraalkoxytitanium to heating, deetherification and polycondensation.

[9] The method according to [6], wherein the organic polytitanoxane composition is obtained by sequentially or simultaneously performing the three steps of:

1) preparing a partially hydrolyzed product by partially hydrolyzing tetrahalotitanium,

2) distilling off a low boiling point component from the partially hydrolyzed product and subjecting the product to polycondensation and

3) reacting the resultant with alcohol, removing HX therefrom and alkoxylating the same.

[10] The method according to any one of [4] to [9], wherein the polytitanoxane composition is used as is or after alkoxy group exchange by reacting the composition with a composition containing at least one member selected from alcohol, an aromatic hydroxy compound and carbonic acid ester.

[11] The method according to any one of [4] to [10], wherein the titanium containing compound contains at least two Ti atoms in one molecule.

[12] The method according to [11], wherein the titanium containing compound contains 2 to 6 Ti atoms in one molecule.

[13] The method according to [11], wherein the titanium containing compound contains at least one Ti—O—Ti bond in a molecule.

[14] The method according to [1], wherein the metal-containing catalyst has a vapor pressure at 230° C. of 10 Pa or lower.

[15] The method according to any one of [1] to [14], wherein the metal-containing catalyst is used in a proportion of 0.0001 to 30% by weight based on the total weight of the starting material and the reactant.

[16] The method according to any one of [1] to [15], wherein the aromatic hydroxy compound is phenol.

[17] Diphenyl carbonate produced by the method according to [16] containing 1 ppm or less of a metal component derived from the metal-containing catalyst.

[18] Polycarbonate comprising the diphenyl carbonate produced by the method according to [16] containing 1 ppm or less of a metal component derived from the metal-containing catalyst.

Although titanium-based catalysts have excellent catalytic action including a good reaction rate and selectivity as described above, it was difficult to separate such titanium catalyst or a titanium containing compound derived from the titanium catalyst from produced diaryl carbonate in the reaction mixture after the reaction and to obtain diaryl carbonate whose titanium content is small. A novel finding that use of a specific titanium catalyst facilitates separation has made it possible for the first time to obtain diaryl carbonate whose titanium content is small without difficulty.

According to the present invention, diaryl carbonate whose titanium content is small can be easily produced without causing problems such as coloring due to titanium.

In the following, the present invention is described in detail. The dialkyl carbonate used in the present invention is represented by the formula (1):

wherein R¹ represents an alkyl group having 1 to 10 carbon atoms, an alicyclic group having 3 to 10 carbon atoms or an aralkyl group having 6 to 10 carbon atoms.

Examples of dialkyl carbonates containing such R¹ include dimethyl carbonate, diethyl carbonate, dipropyl carbonate (and isomers thereof), dibutenyl carbonate (and isomers thereof), dibutyl carbonate (and isomers thereof), dipentyl carbonate (and isomers thereof), dihexyl carbonate (and isomers thereof), diheptyl carbonate (and isomers thereof), dioctyl carbonate (and isomers thereof), dinonyl carbonate (and isomers thereof), didecyl carbonate (and isomers thereof), dicyclopentyl carbonate, dicyclohexyl carbonate, dicycloheptyl carbonate, dibenzyl carbonate, diphenetyl carbonate (and isomers thereof), di(phenylpropyl) carbonate (and isomers thereof), di(phenylbutyl) carbonate (and isomers thereof), di(chlorobenzyl) carbonate (and isomers thereof), di(methoxybenzyl) carbonate (and isomers thereof), di(methoxymethyl) carbonate, di(methoxyethyl) carbonate (and isomers thereof), di(chloroethyl) carbonate (and isomers thereof) and di(cyanoethyl) carbonate (and isomers thereof). Of these dialkyl carbonates, those in which R¹ contains an alkyl group having 1 to 6 carbon atoms are preferably used in the present invention. R¹ is more preferably an n-butyl group, an isobutyl group and an alkyl group having 5 or 6 carbon atoms, and dialkyl carbonate containing a linear or branched alkyl group in which the carbon atom at the a position of oxygen is secondary carbon (—CH₂—) is preferred. Particularly preferred are dibutyl carbonate and bis (2-ethylbutyl) carbonate.

The alkylaryl carbonate used as a starting material in the present invention is represented by the formula (2):

wherein R² may be the same as or different from R¹ and represents an alkyl group having 1 to 10 carbon atoms, an alicyclic group having 3 to 10 carbon atoms or an aralkyl group having 6 to 10 carbon atoms, and Ar² represents an aromatic group having 5 to 30 carbon atoms.

Examples of such R² are groups listed above as R¹. Examples of Ar² include phenyl, tolyl (and isomers thereof), xylyl (and isomers thereof), alkylphenyls groups such as trimethylphenyl (and isomers thereof), tetramethylphenyl (and isomers thereof), ethylphenyl (and isomers thereof), propylphenyl (and isomers thereof), butylphenyl (and isomers thereof), diethylphenyl (and isomers thereof), methylethylphenyl (and isomers thereof), pentylphenyl (and isomers thereof), hexylphenyl (and isomers thereof) and cyclohexylphenyl (and isomers thereof); alkoxyphenyl groups such as methoxyphenyl (and isomers thereof), ethoxyphenyl (and isomers thereof) and buthoxyphenyl (and isomers thereof); halogenated phenyl groups such as fluorophenyl (and isomers thereof), chlorophenyl (and isomers thereof), bromophenyl (and isomers thereof), chloro(methyl)phenyl (and isomers thereof) and dichlorophenyl (and isomers thereof); substituted phenyl groups represented by the following formula (7):

(wherein A represents a bond, a divalent group such as —O—, —S—, —CO— or —SO₂—, an alkylene group or a substituted alkylene group represented by the following (8) or a cycloalkylene group represented by the following (9), and an aromatic ring may be substituted by a lower alkyl group, a lower alkoxy group, an ester group, a hydroxy group, a nitro group, a halogen or a cyano group),

wherein R⁴, R⁵, R⁶ and R⁷ are each independently a hydrogen atom, a lower alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, which may be optionally substituted by a halogen atom or an alkoxy group, and

(wherein k is an integer of 3 to 11 and a hydrogen atom may be substituted by a lower alkyl group, an aryl group or a halogen atom); naphthyl (and isomers thereof), substituted naphthyl groups such as methylnaphthyl (and isomers thereof), dimethylnaphthyl (and isomers thereof), chloronaphthyl (and isomers thereof), methoxynaphthyl (and isomers thereof) and cyanonaphthyl (and isomers thereof); and substituted or unsubstituted heteroaromatic groups such as pyridine (and isomers thereof), cumaryl (and isomers thereof), quinolyl (and isomers thereof), methylpyridyl (and isomers thereof), chloropyridyl (and isomers thereof), methylcumaryl (and isomers thereof) and methylquinolyl (and isomers thereof).

Examples of alkylaryl carbonates containing such R² and Ar² include methyl phenyl carbonate, ethyl phenyl carbonate, propyl phenyl carbonate (and isomers thereof), allyl phenyl carbonate, butyl phenyl carbonate (and isomers thereof), pentyl phenyl carbonate (and isomers thereof), hexyl phenyl carbonate (and isomers thereof), heptyl phenyl carbonate (and isomers thereof), octyl tolyl carbonate (and isomers thereof), nonyl (ethylphenyl) carbonate (and isomers thereof), decyl (butylphenyl) carbonate (and isomers thereof), methyl tolyl carbonate (and isomers thereof), ethyl tolyl carbonate (and isomers thereof), propyl tolyl carbonate (and isomers thereof), butyl tolyl carbonate (and isomers thereof), allyl tolyl carbonate (and isomers thereof), methyl xylyl carbonate (and isomers thereof), methyl (trimethylphenyl) carbonate (and isomers thereof), methyl (chlorophenyl) carbonate (and isomers thereof), methyl (nitrophenyl) carbonate (and isomers thereof), methyl (methoxyphenyl) carbonate (and isomers thereof), methyl cumyl carbonate (and isomers thereof), methyl (naphthyl) carbonate (and isomers thereof), methyl (pyridyl) carbonate (and isomers thereof), ethyl cumyl carbonate (and isomers thereof), methyl (benzoyl phenyl) carbonate (and isomers thereof), ethyl xylyl carbonate (and isomers thereof) and benzyl xylyl carbonate.

Of these alkylaryl carbonates, those in which R² is an alkyl group having 1 to 6 carbon atoms, and more preferably R¹ is n-butyl, isobutyl or an alkyl group having 5 to 6 carbon atoms and Ar² is an aromatic group having 6 to 10 carbon atoms are more preferably used. Particularly preferred are butyl phenyl carbonate and (2-ethylbutyl)phenyl carbonate. The starting material used in the present invention is selected from the group consisting of a dialkyl carbonate represented by the above-described formula (1), an alkylaryl carbonate represented by the formula (2) and a mixture thereof.

The aromatic monohydroxy compound used as a reactant in the present invention is represented by the following formula (3), and any compound may be used as long as a hydroxyl group is directly bonded to the aromatic group.

Ar¹OH  (3)

In the formula, Ar¹ may be the same as or different from Ar² and represents an aromatic group having 5 to 30 carbon atoms. Examples of such Ar¹ are those listed above as Ar².

Examples of aromatic monohydroxy compounds having such Ar¹ include phenol, alkylphenols such as cresol (and isomers thereof), xylenol (and isomers thereof), trimethylphenol (and isomers thereof), tetramethylphenol (and isomers thereof), ethylphenol (and isomers thereof), propylphenol (and isomers thereof), butylphenol (and isomers thereof), diethylphenol (and isomers thereof), methylethylphenol (and isomers thereof), methylpropylphenol (and isomers thereof), dipropylphenol (and isomers thereof), methylbutylphenol (and isomers thereof), pentylphenol (and isomers thereof), hexylphenol (and isomers thereof) and cyclohexylphenol (and isomers thereof); alkoxyphenols such as methoxyphenol (and isomers thereof) and ethoxyphenol (and isomers thereof); substituted phenols represented by the formula (10):

(wherein A is a group as defined above); naphthol (and isomers thereof) and substituted naphthols; and monohydroxy heteroaromatic compounds such as hydroxypyridine (and isomers thereof), hydroxycoumarin (and isomers thereof) and hydroxyquinoline (and isomers thereof). Of these aromatic mono hydroxy compounds, aromatic mono hydroxy compounds whose Ar¹ is an aromatic group having 6 to 10 carbon atoms are preferred in the present invention, and phenol is particularly preferred.

The alkylaryl carbonate used as a reactant in the present invention is represented by the following formula (4).

In the formula, R³ may be the same as or different from R¹ and R², and represents an alkyl group having 1 to 10 carbon atoms, an alicyclic group having 3 to 10 carbon atoms or an aralkyl group having 6 to 10 carbon atoms, and Ar³ may be the same as or different from Ar¹ and Ar², and represents an aromatic group having 5 to 30 carbon atoms. Examples of such R³ are groups listed above as R¹, and examples of Ar³ are those listed above as Ar².

Examples of alkylaryl carbonates containing such R³ and Ar³ are those listed above as in the formula (2). Of these alkylaryl carbonates, those whose R³ has an alkyl group having 1 to 6 carbon atoms and Ar³ is an aromatic group having 6 to 10 carbon atoms are preferably used. R³ is more preferably an n-butyl group, an isobutyl group or a linear or branched alkyl group having 5 to 6 carbon atoms in which the carbon atom at the a position of oxygen is secondary carbon (—CH₂—). Particularly preferred are butyl phenyl carbonate and (2-ethylbutyl)phenyl carbonate.

The reactant of the present invention is selected from the group consisting of an aromatic monohydroxy compound represented by the formula (3), an alkylaryl carbonate represented by the formula (4) and a mixture thereof. The method of the present invention for producing an aromatic carbonate or an aromatic carbonate mixture, which comprises allowing to react a starting material and a reactant in the presence of a metal-containing catalyst typically involves the reactions of the formulas (E1), (E2), (E3) and (E4).

(In the formulas, R¹, R², R³, Ar¹, Ar² and Ar³ are as defined above; in the reaction formula (E4), Ar independently represents Ar² or Ar³ and R independently represents R² or R³; when R²═R³ and Ar²═Ar³ in the reaction formula (E4), the reaction is an transesterification between the same kind of molecules, which may also be generally referred to as a disproportionation reaction.)

When carrying out reactions of the formulas (E1), (E2), (E3) and (E4) according to the method of the present invention, one or at least two dialkyl carbonates and alkylaryl carbonates may be used as starting materials. Further, one or at least two aromatic monohydroxy compounds and alkylaryl carbonates may be used as reactants.

A case in which R²═R³═R and Ar²═Ar³═Ar in the transesterification represented by the reaction formula (E4) is preferred because diaryl carbonate and dialkyl carbonate are obtained by an transesterification of the same kind of molecules of one alkylaryl carbonate. Further, when R¹═R²═R³═R and Ar¹═Ar²═Ar³═Ar in the reaction formulas (E1) and (E4), diaryl carbonate is obtained from dialkyl carbonate and an aromatic monohydroxy compound through alkylaryl carbonate as described in the following reaction formulas (E5) and (E6) by combining the reaction represented by the reaction formula (E1) and the reaction represented by the reaction formula (E4), and this is a particularly preferred embodiment of the present invention.

When dialkyl carbonate produced as a by-product in the reaction represented by the reaction formula (E6) is reused as a raw material of the reaction represented by the reaction formula (E5), 1 mole of diaryl carbonate and 2 moles of aliphatic alcohol are produced from 1 mole of dialkyl carbonate and 2 moles of an aromatic monohydroxy compound. In the above-described reaction formula (E5), when R is selected from n-butyl, iso-butyl and an alkyl group having 5 to 6 carbon atoms and Ar═C₆H₅, by-product alcohol has the lowest boiling point in the reaction system and forms no azeotrope with dialkyl carbonate which is a reactant. This case is particularly advantageous because the reaction proceeds efficiently and easily produces diphenyl carbonate which is an important raw material of polycarbonate and isocyanate.

The metal-containing catalyst used in the present invention means a specific metal-containing catalyst which facilitates the aforementioned reactions of the reaction formulas (E1) to (E4), has a molecular weight of 450 or more, more preferably a molecular weight of 480 or more, and is in the form of liquid (under the above-described reaction conditions) or dissolved in the liquid phase of the reaction system. The metal-containing catalyst is preferably a titanium containing compound containing titanium. Examples of preferred titanium containing compounds in the form of liquid under the above-described reaction conditions or dissolved in the liquid phase of the reaction system include organopolytitanoxane composition such as polyorthotitanate and condensed orthotitanate. It is preferred that the organic polytitanoxane has at least one alkoxy group and/or aryloxy group as an organic group.

When the metal-containing catalyst is a metal-containing catalyst containing titanium and/or a metal-containing catalyst having a vapor pressure at 230° C. of 10 Pa or lower and containing titanium, the catalyst preferably contains at least two Ti atoms in one molecule, more preferably 2 to 6 Ti atoms in one molecule. When the metal-containing catalyst contains 2 or more Ti atoms in one molecule, the compound contains at least one Ti—O—Ti bond in one molecule. When the metal-containing catalyst contains Sn, it contains at least 3 Sn atoms.

Examples of such compounds include metal-containing catalysts represented by the following formulas (11), (12) and (13), titanate oligomers containing at least one titanoxane structure (Ti—O—Ti bond) (e.g., titanium compounds represented by the following formula (14)) in one molecule and tin compounds represented by the following formula (15). Since the above-described metal-containing catalysts are easily associated, they may be in the form of a monomer, in an associated form, or an adduct or an associated form with alcohol or an aromatic hydroxy compound. These catalytic components may be a product of a reaction with an organic compound present in the reaction system, e.g., aliphatic alcohols, an aromatic monohydroxy compounds, alkylaryl carbonates, diaryl carbonates or dialkyl carbonates, or may be heated in the form of a raw material or a product prior to the reaction. The titanium compound represented by the formula (11) and/or the formula (14) (e.g., when R⁴⁴ to R⁶¹ in the formula (14) are aromatic groups (e.g., phenyl group)) tends to form an adduct particularly with an aromatic hydroxy compound. The structure of the adduct is unknown by the present analytical methods, but the structure represented by the following formula has a molecular weight of 450 or more, more preferably a molecular weight of 480 or more, excluding the molecular weight of the molecules involved in the formation of an adduct. Such molecules involved in the formation of an adduct may be identified by a method such as NMR, or the aromatic hydroxy compound involved in the formation of an adduct may be removed by a known method (e.g., recrystallization using solvent described in J. Indian. Chem. Soc., Vol. 38, No. 3, 147-152 (1961)).

In the formula (11), R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, and R²⁷ independently represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, X₁ and X₂ represent an alkyl group, an aralkyl group or an aryl group; R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶ and R²⁷ are not simultaneously a hydrogen atom, and at least four of them are an alkyl group, an aralkyl group or an aryl group; R²⁸, R²⁹, R³⁰, R³¹, R³², R³³, R³⁴ and R³⁵ may be covalently bonded within the range that the molecular weight is 450 or more, and more preferably 480 or more)

(In the formula (12), R²⁸, R²⁹, R³⁰, R³¹, R³², R³³, R³⁴ and R³⁵ independently represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group; X₁ and X₂ represent an alkyl group, an aralkyl group and an aryl group; at least two of R²⁸, R²⁹, R³⁰, R³¹, R³², R³³, R³⁴, R³⁵, X₁ and X₂ are an aralkyl group or an aryl group.)

(In the formula (13), R³⁶, R³⁷, R³⁸, R³⁹, R⁴⁰, R⁴¹, R⁴² and R⁴³ independently represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, at least two of them are an aralkyl group or an aryl group, and these R³⁶ to R⁴³ may be bonded with each other.)

(In the formula (14), R⁴⁴, R⁴⁵, R⁴⁶, R⁴⁷, R⁴⁸, R⁴⁹, R⁵⁰, R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵, R⁵⁶, R⁵⁷, R⁵⁸, R⁵⁹, R⁶⁰, and R⁶¹ independently represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group or an acyl group, a, b, c, d, e and f independently represent an integer of 0 to 4, and R⁴⁴, R⁴⁵, R⁴⁶, R⁴⁷, R⁴⁸, R⁴⁹, R⁵⁰, R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵, R⁵⁶, R⁵⁷, R⁵⁸, R⁵⁹, R⁶⁰ and R⁶¹ in the formula (14) each may be covalently bonded.)

(In the formula (15), R⁶² is an alkyl group, an aralkyl group or an aryl group having 4 or more carbon atoms, R⁶³, R⁶⁴, R⁶⁵, R⁶⁶ and R⁶⁷ independently represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group or an acyl group, g represents an integer of 1 or more, and R⁶³, R⁶⁴, R⁶⁵, R⁶⁶ and R⁶⁷ in the formula (15) each may be covalently bonded.)

Examples of alkyl groups represented by R⁸ to R⁶¹ include linear or cyclic alkyl groups having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group (and isomers thereof), a butyl group (and isomers thereof), a pentyl group (and isomers thereof), a hexyl group (and isomers thereof), a heptyl group (and isomers thereof), an octyl group (and isomers thereof), a nonyl group (and isomers thereof), a decyl group (and isomers thereof), a cyclobutyl group, a cyclopentyl group (and isomers thereof) and a cyclohexyl group (and isomers thereof). Those containing an ether bond are also useful, and examples thereof include a methoxyethyl group (and isomers thereof), an ethoxyethyl group (and isomers thereof), a methoxypropyl group (and isomers thereof), an ethoxypropyl group (and isomers thereof), a methoxybutyl group (and isomers thereof) and an ethoxybutyl group (and isomers thereof).

Examples of aralkyl groups represented by R⁸ to R⁶¹ include aralkyl groups having 7 to 12 carbon atoms which may have a substituent, such as a benzyl group and a phenylethyl group.

Examples of aryl groups represented by R⁸ to R⁶¹ include phenyl or alkylphenyl groups such as phenyl, tolyl (and isomers thereof), xylyl (and isomers thereof), trimethylphenyl (and isomers thereof), tetramethylphenyl (and isomers thereof), ethylphenyl (and isomers thereof), propylphenyl (and isomers thereof), butylphenyl (and isomers thereof), diethylphenyl (and isomers thereof), methylethylphenyl (and isomers thereof), pentylphenyl (and isomers thereof), hexylphenyl (and isomers thereof) and cyclohexylphenyl (and isomers thereof); alkoxyphenyl groups such as methoxyphenyl (and isomers thereof), ethoxyphenyl (and isomers thereof) and butoxyphenyl (and isomers thereof); halogenated phenyl groups such as fluorophenyl (and isomers thereof), chlorophenyl (and isomers thereof), bromophenyl (and isomers thereof), chloro(methyl)phenyl (and isomers thereof) and dichlorophenyl (and isomers thereof); substituted phenyl groups represented by the following formula (16):

(wherein B represents a bond, a divalent group such as —O—, —S—, —CO— and —SO₂—, an alkylene group or a substituted alkylene group represented by the following (17) or a cycloalkylene group represented by the following (18), and an aromatic ring may be substituted by a lower alkyl group, a lower alkoxy group, an ester group, a hydroxy group, a nitro group, a halogen or a cyano group),

(wherein R⁶⁸, R⁶⁹, R⁷⁰ and R⁷¹ are each independently a hydrogen atom, a lower alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, which may be optionally substituted by a halogen atom or an alkoxy group), and

(wherein m is an integer of 3 to 11 and a hydrogen atom may be substituted by a lower alkyl group, an aryl group or a halogen atom); naphthyl (and isomers thereof), substituted naphthyl groups such as methylnaphthyl (and isomers thereof), dimethylnaphthyl (and isomers thereof), chloronaphthyl (and isomers thereof), methoxynaphthyl (and isomers thereof) and cyanonaphthyl (and isomers thereof); and substituted or unsubstituted heteroaromatic groups such as pyridine (and isomers thereof), cumaryl (and isomers thereof), quinolyl (and isomers thereof), methylpyridyl (and isomers thereof), chloropyridyl (and isomers thereof), methylcumaryl (and isomers thereof) and methylquinolyl (and isomers thereof).

The aryl group represented by R⁸ to R⁶¹ may also be a hydroxy substituted aryl group which is represented by the following formula (19):

Ar⁴—(OH)_(n)  (19)

(wherein Ar⁴ represent an aromatic group having a valence of n, n is an integer of 2 or more, and each —OH group may be bonded to any position of Ar⁴).

The residue of the aromatic polyhydroxy compound is represented by the following formula (20) and is chemically bonded to at least one member selected from the group consisting of metal of metal-containing catalyst, an alkoxycarbonyl group derived from dialkyl carbonate or alkylaryl carbonate, an aryloxycarbonyl group derived from alkylaryl carbonate or diaryl carbonate and a carbonyl group derived from dialkyl carbonate, alkylaryl carbonate or diaryl carbonate,

—(O)_(n)—Ar⁴—(OH)_(n-p)  (20)

(wherein Ar⁴ and n are as described above, p is an integer of 1 to m, and an —OH group and an —O— group may be bonded to any position of the aromatic ring of Ar⁴)

Examples of Ar⁴ in the formula (19) and (20) include aromatic groups represented by the following formulas (21), (22), (23), (24) and (25):

(wherein Q¹ is a single bond, a divalent alkylene group having 1 to 30 carbon atoms or a divalent group selected from —O—, —CO—, —S—, —SO₂—, —SO— and —COO—);

(wherein Q¹ is as defined above and each Q¹ may be the same or different); and

(wherein Q² represents a tri-valent group such as a tri-valent alkanetriyl group having 1 to 30 carbon atoms or a tri-valent aromatic group; at least one hydrogen atom on an aromatic ring may be substituted by another substituent such as a halogen atom, an alkoxy group having 1 to 30 carbon atoms, a phenyl group, a phenoxy group, a vinyl group, a cyano group, an ester group, an amide group or a nitro group).

Examples of such hydroxy substituted aryl groups include hydroxyphenyl (and isomers thereof), dihydroxyphenyl (and isomers thereof), trihydroxyphenyl (and isomers thereof), hydroxytolyl (and isomers thereof), hydroxyxylyl (and isomers thereof), [1-(hydroxyphenyl)-1-methyl-ethyl]-phenyl (and isomers thereof), [4-(hydroxybenzyl)]-phenyl (and isomers thereof), (hydroxy-phenoxy)-phenyl (and isomers thereof), hydroxybenzoyl-phenyl (and isomers thereof), hydroxybiphenyl (and isomers thereof), 2-(hydroxyphenyl)-hydroxypropyl-phenyl, tri-(hydroxyphenyl)-phenyl (and isomers thereof), hydroxynaphthyl (and isomers thereof) and trihydroxynaphthyl (and isomers thereof).

Examples of acyl groups include acyl groups represented by the following formula (26):

(wherein Ar⁵ represents an aromatic group).

Examples of aromatic group represented by Ar⁵ include phenyl or alkylphenyl groups such as phenyl, tolyl (and isomers thereof), xylyl (and isomers thereof), trimethylphenyl (and isomers thereof), tetramethylphenyl (and isomers thereof), ethylphenyl (and isomers thereof), propylphenyl (and isomers thereof), butylphenyl (and isomers thereof), diethylphenyl (and isomers thereof), methylethylphenyl (and isomers thereof), pentylphenyl (and isomers thereof), hexylphenyl (and isomers thereof) and cyclohexyl phenyl (and isomers thereof); alkoxyphenyl groups such as methoxyphenyl (and isomers thereof), ethoxyphenyl (and isomers thereof) and butoxyphenyl (and isomers thereof); halogenated phenyl groups such as fluorophenyl (and isomers thereof), chlorophenyl (and isomers thereof), bromophenyl (and isomers thereof), chloro(methyl)phenyl (and isomers thereof) and dichlorophenyl (and isomers thereof) and substituted phenyl groups represented by the aforementioned formulas (16), (19) and (20).

Examples of such acyl groups include a benzoyl group, a phthaloyl group, a terephthaloyl group and a salicyl group.

The same kinds of groups as those selected from R¹, R², R³, Ar¹, Ar² and Ar³ of the starting material and/or the reactant are preferred as the groups of R⁴⁴˜R⁶¹ because kinds of products can be reduced. In case of the compound represented by formula (11), they are R⁸˜R²⁷ when the molecular weight of the compound is 450 or more, and more preferably 480 or more. In case of the compound represented by formula (14), the groups of R⁴⁴˜R⁶¹ are selected so that the molecular weight of the compound is 450 or more, and more preferably 480 or more.

Examples of alkyl groups represented by R⁶² in the formula (15) include a linear or cyclic alkyl group having 4 to 10 carbon atoms such as a butyl group (and isomers thereof), a penthyl group (and isomers thereof), a hexyl group (and isomers thereof), a heptyl group (and isomers thereof), an octyl group (and isomers thereof), a nonyl group (and isomers thereof), a decyl group (and isomers thereof), a cyclobutyl group, a cyclopentyl group (and isomers thereof) and a cyclohexyl group (and isomers thereof). Those containing an ether bond are also useful, and examples thereof include a methoxyethyl group (and isomers thereof), an ethoxyethyl group (and isomers thereof), a methoxypropyl group (and isomers thereof), an ethoxypropyl group (and isomers thereof), a methoxybutyl group (and isomers thereof) and an ethoxybutyl group (and isomers thereof).

Examples of aralkyl groups represented by R⁶² include aralkyl groups having 7 to 12 carbon atoms which may have a substituent, such as a benzyl group and a phenylethyl group.

Examples of aryl groups represented by R⁶² include phenyl or alkylphenyl groups such as phenyl, tolyl (and isomers thereof), xylyl (and isomers thereof), trimethylphenyl (and isomers thereof), tetramethylphenyl (and isomers thereof), ethylphenyl (and isomers thereof), propylphenyl (and isomers thereof), butylphenyl (and isomers thereof), diethylphenyl (and isomers thereof), methylethylphenyl (and isomers thereof), pentylphenyl (and isomers thereof), hexylphenyl (and isomers thereof) and cyclohexylphenyl (and isomers thereof); alkoxyphenyl groups such as methoxyphenyl (and isomers thereof), ethoxyphenyl (and isomers thereof) and butoxyphenyl (and isomers thereof); halogenated phenyl groups such as fluorophenyl (and isomers thereof), chlorophenyl (and isomers thereof), bromophenyl (and isomers thereof), chloro(methyl)phenyl (and isomers thereof) and dichlorophenyl (and isomers thereof).

Examples of R⁶³ to R⁶⁷ in the formula (15) include alkyl groups, aralkyl groups and aryl groups listed above as examples of R⁸ to R⁶¹.

The same kinds of groups as those selected from R¹, R², R³, Ar¹, Ar² and Ar³ of the starting material and/or the reactant are preferred because kinds of products can be reduced.

Examples of compounds represented by the formula (11) include titanium methylphenoxide: Ti(OPhMe)₄ and titanium dimethylphenoxide: Ti(OPh(Me)₂)₄.

The compound represented by the formula (12) has a valence of Ti of 4, and the compound may contain alcohol or aromatic alcohol as a ligand in the form of alcoholate or phenolate. Examples of compounds of the formula (12) include compounds of the following formula (27).

Examples of compounds represented by the formula (13) include titanium-disalicylate, titanium-bis(2-methyl salicylate) and titanium-bis(3-methyl salicylate).

Of the titanium containing compounds, an organic polytitanoxane composition produced by a known method may be used. Such known methods include a method in which titanium alkoxide is partially hydrolyzed and subjected to polycondensation while removing alcohol (e.g., Journal of Polymer Science, vol. VII, No. 6, 591-602). Examples of such polytitanoxane compositions also include ladder polytitanoxane obtained by the method described in JP-A-1-129031 and cyclic titanoxane obtained by the method described in JP-A-1-31793, JP-A-1-52786 and JP-A-64-52786.

Further, a copolymer with another metal alkoxide obtained by the method described in JP-B-5-31900 may be also used. Polytitanoxane or copolytitanoxane having 2 or more, preferably 2 to 6, more preferably 4 to 6 Ti atoms in a molecule is preferably used. These polytitanoxane and copolytitanoxane may contain at least one Ti—O—Ti bond in a molecule. Although analysis of Ti—O—Ti bonds is extremely difficult, researchers in this field now consider that a Ti—O—Ti bond is formed when titanium alkoxide described above is partially hydrolyzed and subjected to polycondensation with removing alcohol, and the present invention also follows this argument. Specifically, as shown in the following formula (28), one Ti—O—Ti bond is formed by partially hydrolyzing titanium(tetraalkoxide) by adding one molecule of water per two molecules of titanium(tetraalkoxide) and then removing two molecules of alcohol.

Further, in the case of a oligomerization reaction, polytitanoxane having a few Ti—O—Ti bonds in a molecule can be obtained by adding water in an amount suitable for the oligomerization degree and removing produced alcohol. In order to obtain a titanium compound containing 2 to 6 Ti atoms in a molecule, tetraalkoxytitanium is partially hydrolyzed by water of not more than 0.1 to 2-fold mole in a molar ratio relative to Ti atoms, preferably by water of not more than 0.3 to 1.5-fold mole, more preferably by water of not more than 0.5 to 1.2-fold mole in order to avoid generation of solid components caused by excessive partial hydrolysis; and then can be obtained by the polycondensation which removes low boiling point components. The amount of water used for partial hydrolysis described above is based on the total amount of tetraalkoxytitanium used for producing an organic polytitanoxane composition. All of water necessary for partial hydrolysis may be used for partial hydrolysis of part of the tetraalkoxytitanium used for production, and then the rest of the tetraalkoxytitanium is added thereto to perform a reaction. In this case, an organic polytitanoxane composition containing many branched structures can be obtained. Solid components generated during partial hydrolysis may be removed by filtration. Referring to the partial hydrolysis, tetraalkoxytitanium is dissolved in an alcohol solvent and the solution is cooled to 80° C. or lower, preferably 5° C. or lower, then alcohol containing a desired amount of water is added thereto dropwise over 1 to 5 hours under stirring, the solution temperature is adjusted to 30° C. to 150° C., and the low boiling point components are removed by distillation. The reaction may be terminated when alcohol is no longer extracted. A known reactor may be used, and preferred is a stirring vessel in which cooling and heating can be performed. Thus, in the method of producing organic polytitanoxane of the present invention, organic polytitanoxane can be obtained by sequentially or simultaneously performing the two steps of: 1) preparing a partially hydrolyzed product by partially hydrolyzing tetraalkoxytitanium and 2) removing the generated low boiling point component including alcohol from the partially hydrolyzed product and subjecting the product to polycondensation.

Alternatively, an organic polytitanoxane composition may be obtained by partially hydrolyzing tetrahalotitanium (TiX₄: X═Cl, Br), removing —HX therefrom and subjecting the resultant to a polycondensation reaction, or by removing —HX from titanium hydroxide and tetrahalotitanium and subjecting the resultant to a polycondensation reaction. Also preferred is an organic polytitanoxane composition obtained by sequentially or simultaneously performing the three steps of: 1) preparing a partially hydrolyzed product by partially hydrolyzing tetrahalotitanium, 2) removing a low boiling point component from the partially hydrolyzed product and subjecting the product to polycondensation and 3) reacting the resultant with alcohol, removing HX therefrom and alkoxylating the same.

It is also possible to dealcoholize titanium hydroxide and tetraalkoxytitanium and subject the resultant to polycondensation.

Another well-known method for producing an organic titanoxane composition comprises subjecting tetraalkoxytitanium to heating, deetherification and polycondensation. Preferably used is an organic polytitanoxane composition obtained after removing 0.1 to 2-fold mole, preferably 0.3 to 1.5-fold mole, more preferably 0.5 to 1.2-fold mole of ether based on titanium atoms contained in tetraalkoxytitanium at a deetherification temperature of 100° C. to 300° C., preferably 150° C. to 250° C. over 1 to 300 hours.

These known organic polytitanoxanes obtained by a polycondensation reaction of at least one raw material selected from tetraalkoxytitanium, tetrahalotitanium (TiX₄: X being selected from Cl and Br) and titanium hydroxide can be used in the present invention.

The above-described organic polytitanoxane and metal-containing catalyst may be used as is, or after exchange of organic groups before use. For example, they may be used after exchange of alkoxy groups by reacting with a composition containing at least one component selected from alcohol, an aromatic hydroxy compound and carbonic acid ester. In other words, they may be used after mixing or reacting with a starting material, a reactant or a by-product of an transesterification or a disproportionation reaction in the present invention.

When a conventional organic titanate is used, more specifically when dimethyl carbonate is used as a starting material, phenol is used as a reactant and phenyl titanate [Ph(OPh)₄] (phenol adduct also usable) is used as organic titanate to produce an aromatic carbonate, specifically, methyl phenyl carbonate, methyl titanate [Ti(OMe)₄] may be generated in the distillation column in the equilibrium reaction due to alkoxy exchange. Since methyl titanate is hardly soluble in the reaction mixture and is subliming, it may adhere to the wall of the distillation column to cause clogging. Surprisingly, however, it has been found that the organic polytitanoxane composition (titanate oligomer, etc.) used in the present invention hardly causes such poor solubility or adhesion to walls due to sublimation.

Whether a Ti—O—Ti bond is present or not may be simply confirmed by elemental analysis of the catalyst and NMR. When the structure of an organic group bonded or coordinated to Ti is known, the amount of bridging oxygen derived from Ti—O—Ti can be determined by subtracting the amount of oxygen atoms derived from the organic group from the elemental analysis value. The number of bridging oxygen involved in Ti—O—Ti bonds and the number of the bonds may be determined from the ratio of the amount of Ti atoms to the amount of bridging oxygen. In addition, the valence of Ti and the number of oxygen atoms involved in Ti—O—Ti may be determined by known X-ray crystallographic analysis (e.g., JP-A-2004-256719), assuming that a Ti—O bond is present when the atomic distance between Ti and O is smaller than the sum (2.87 Å) of the ionic radii of Ti atom and oxygen atom.

In addition, such polytitanoxane or copolytitanoxane obtained by a known method may be alkoxy-substituted by reacting with alcohol or an aromatic hydroxy compound by a known method (e.g., J. inorg. nucl. Chem., Vol. 28, 2410 (1966), J. Indian Chem. Soc., Vol. 38, No. 3, p 147-152 (1961)). These catalytic components may be a product of a reaction with an organic compound present in the reaction system, e.g., aliphatic alcohols, aromatic monohydroxy compounds, alkylaryl carbonates, diaryl carbonates or dialkyl carbonates or may be heated prior to the reaction in the form of a raw material or a product, or low boiling point components may be removed therefrom upon heating. The catalyst may be an adduct or an associated form with alcohol or an aromatic hydroxy compound present in the reaction system.

The structure of polytitanoxane obtained by the above-mentioned method is shown in the above-described formula (14).

Examples of such titanium compounds include 1) linear polytitanate represented by the following formula (29) and cyclic polytitanate represented by the following formula (30).

(In the formula (29), R⁷² represents an alkyl group having 1 to 10 carbon atoms, an aralkyl, aryl or acyl group, R⁷² may be the same or different from each other or may be bonded with each other, and h is an integer of 1 to 5).

(In the formula (30), R⁷³ represents an alkyl group having 1 to 10 carbon atoms, an aralkyl, aryl or acyl group, R⁷³ may be the same or different from each other or may be bonded with each other, and i is an integer of 1 to 4, j is an integer of 0 to 4, and i+j=4.)

When R⁷² in the formula (29) and R⁷³ in the formula (30) have a small number of carbon atoms, the catalyst itself may not be in the form of liquid, or may not be in the form of liquid in the reaction system because it has extremely low solubility in the liquid phase of the reaction system. Thus, preferred examples of R⁷² and R⁷³ are an alkyl group having 3 to 10 carbon atoms such as a propyl group (and isomers thereof), a butyl group (and isomers thereof), a pentyl group (and isomers thereof), a hexyl group (and isomers thereof), a heptyl group (and isomers thereof), an octyl group (and isomers thereof), a nonyl group (and isomers thereof), a decyl group (and isomers thereof), a cyclobutyl group, a cyclopentyl group (and isomers thereof) and a cyclohexyl group (and isomers thereof). Those containing an ether bond are also useful, and examples thereof include alkyl groups such as a methoxyethyl group (and isomers thereof), an ethoxyethyl group (and isomers thereof), a methoxypropyl group (and isomers thereof), an ethoxypropyl group (and isomers thereof), a methoxybutyl group (and isomers thereof) and an ethoxybutyl group (and isomers thereof). Preferred examples thereof also include aralkyl groups having 7 to 12 carbon atoms which may have a substituent, such as a benzyl group and a phenylethyl group. Preferred examples thereof also include aryl groups, e.g. phenyl or alkylphenyl groups such as phenyl, tolyl (and isomers thereof), xylyl (and isomers thereof), trimethylphenyl (and isomers thereof), tetramethylphenyl (and isomers thereof), ethylphenyl (and isomers thereof), propylphenyl (and isomers thereof), butylphenyl (and isomers thereof), diethylphenyl (and isomers thereof), methylethylphenyl (and isomers thereof), pentylphenyl (and isomers thereof), hexylphenyl (and isomers thereof) and cyclohexylphenyl (and isomers thereof); alkoxyphenyl groups such as methoxyphenyl (and isomers thereof), ethoxyphenyl (and isomers thereof) and butoxyphenyl (and isomers thereof); halogenated phenyl groups such as fluorophenyl (and isomers thereof), chlorophenyl (and isomers thereof), bromophenyl (and isomers thereof), chloro(methyl)phenyl (and isomers thereof) and dichlorophenyl (and isomers thereof).

Examples of such compounds include compounds whose structural formula is as described below, e.g., butoxy titanate dimer, phenoxy titanate oligomers such as phenoxy titanate dimer, phenoxy titanate trimer and phenoxy titanate tetramer (and isomers thereof), phenoxy salicyl titanate oligomers such as phenoxy-salicyl-titanate dimer and phenoxy-salicyl-titanate trimer, titanate dimer (derived from phenol and bisphenol A) and titanate trimer (derived from phenol and bisphenol A). Compounds containing 2 to 6 Ti atoms in a molecule are preferred in terms of their solubility. Titanate oligomers have molecular weight distribution, and they may contain a component which does not satisfy the molecular weight of 450 or more defined in the present invention, or contain a component whose vapor pressure at 230° C. is 10 Pa or higher. Such titanate oligomers may be used as is, but they may be used after removing low boiling point components or low molecular weight components by distillation.

These catalytic components may be a product of a reaction with an organic compound present in the reaction system, e.g., aliphatic alcohol, an aromatic monohydroxy compound, alkylaryl carbonate, diaryl carbonate or dialkyl carbonate or may be heated prior to the reaction in the form of a raw material or a product, or low boiling point components may be removed therefrom upon heating.

Examples of compounds represented by the formula (15) include monoalkyltin (IV) alkoxide oxide. Among the scientists of the research field concerned, it is a common knowledge that no Sn═O double bond is generally present and monoalkyltin (IV) alkoxide oxide is usually present in the form of an oligomer of bonded molecules. Examples of such compounds include butyltin (IV) butyloxide oxide, butyltin (IV) (2-ethylbutyloxide) oxide, butyltin (IV) (3-methoxypropyloxide) oxide, butyltin (IV) (2-methoxyethoxide) oxide, butyltin (IV) (2-ethoxyethoxide) oxide, butyltin (IV) phenoxide oxide, octyltin (IV) butyloxide oxide, octyltin (IV) (2-ethylbutyloxide) oxide, octyltin (IV) (3-methoxypropyloxide) oxide, octyltin (IV) (2-methoxyethoxide) oxide, octyltin (IV) (2-ethoxyethoxide) oxide and octyltin (IV) phenoxide oxide.

The types of the reaction vessel used in the present invention are not particular limited, and any conventional reaction vessel such as a stirring vessel, a multi-stage stirring vessel, a multi-stage distillation column or a combination of these may be used. These reaction vessels may be used for either a batchwise reaction or a continuous reaction. In order to efficiently shift the equilibrium of the reaction in the direction of the product system, a process using a multi-stage distillation column is preferred, and a continuous process using a multi-stage distillation column is more preferred. Multi-stage distillation columns have two or more theoretical distillation stages, and any type may be used as long as it is capable of performing continuous distillation.

As such a multi-stage distillation column, any generally used multi-stage distillation column may be used, and examples thereof include plate type columns using a tray such as a bubble-cap tray, a sieve tray, a valve tray or a counterflow tray, and packed type columns packed with any of various packings such as a Raschig ring, a Lessing ring, a Pall ring, a Berl saddle, an Interlox saddle, a Dixon packing, a McMahon packing, a Heli pack, a Sulzer packing and Mellapak. Further, a plate-packed column combined type having both a plate column section and a packed column section with packings may also be preferably used. When a continuous process using a multi-stage distillation column is applied to the production of aromatic carbonates, starting materials and reactants are supplied to a continuous multi-stage distillation column and these materials are allowed to react with each other in the presence of a metal-containing catalyst in a liquid phase or in a gas-liquid phase in the distillation column while simultaneously extracting the produced high boiling point reaction mixture containing aromatic carbonate or an aromatic carbonate mixture in a liquid form from the bottom of the column, while continuously distilling off the produced low boiling point reaction mixture containing a by-product in the form of gas from the upper part of the distillation column by distillation.

The catalyst in the present invention is used in a proportion of usually 0.0001 to 30% by weight, preferably 0.001 to 10% by weight, more preferably 0.01 to 5% by weight based on the total weight of the raw materials, although the proportion depends on the kind of the catalyst used, the kind and the amount of raw materials and reaction conditions such as reaction temperature and reaction pressure. The reaction time (residence time in a continuous process) in the present invention is not particular limited, and is usually 0.001 to 50 hours, preferably 0.01 to 10 hours, more preferably 0.05 to 5 hours.

The reaction is performed at a reaction temperature of usually 50 to 350° C., preferably 100 to 280° C. depending on the kind of raw material compounds used. The reaction is performed under reduced pressure, atmospheric pressure or increased pressure, usually at 0.1 to 2.0×10⁷ Pa depending on the kind of the raw material compounds used and the reaction temperature. In the present invention, it is not always necessary to use a reaction solvent, but an appropriate inert solvent such as ether, aliphatic hydrocarbon, aromatic hydrocarbon or halogenated aromatic hydrocarbon may be used as a reaction solvent in order to facilitate the reaction procedure.

The present invention has a feature that liquid containing high boiling point materials and a metal-containing catalyst is removed from the reaction system and produced aromatic carbonate is transported in the form of gas, and the liquid containing the metal-containing catalyst is recycled in the system.

In this process, part of the liquid containing a metal-containing catalyst may be blown down and a fresh catalyst may be added to the liquid. Also, the liquid may be reacted with an active substance to produce a reaction mixture of a substance derived from a high boiling point material and a substance derived from a metal-containing catalyst, and the mixture is separated into a component composed mainly of a substance derived from a high boiling point material and a component composed mainly of a substance derived from a metal-containing catalyst, and the substance derived from a metal-containing catalyst may be recycled in the system.

The term “reaction system” refers to the space inside the reactor, piping and equipment surrounding the reactor, equipment and piping for the catalyst recovery system. The “liquid containing a high boiling point material and a metal-containing catalyst” in the present invention refers to liquid containing a catalyst and a high boiling point material supplied to the reactor, a reaction mixture containing a catalyst and a high boiling point material present in the reactor, a reaction mixture containing a catalyst and a high boiling point material discharged from the reactor and a concentrated liquid having increased concentration of a catalyst and a high boiling point material by evaporation of part of the reaction mixture. The catalyst may be completely dissolved in the liquid or present in the form of slurry. In the case of slurry, undissolved portions in the slurry are also included in the “liquid containing a high boiling point material and a metal-containing catalyst”.

The “high boiling point material” in the present invention is an organic substance whose boiling point is the same as or higher than that of aromatic carbonate produced in the present invention. Examples thereof include aromatic polyhydroxy compounds and residues thereof, aromatic carboxyl compounds and residues thereof and xanthones. Another example of such high boiling point material is a high molecular weight by-product produced by an additional reaction of the above-described aromatic polyhydroxy compounds and residues thereof, aromatic carboxyl compounds and residues thereof and xanthones.

The aromatic polyhydroxy compound is represented by the following formula (31):

Ar⁶—(OH)_(q)  (31)

(wherein Ar⁶ is an aromatic group having a valence of q, q is an integer of 2 or more, and each —OH group may be bonded to any position of Ar⁶ group).

The residue of the aromatic polyhydroxy compound is represented by the following formula (32) and is chemically bonded to at least one member selected from the group consisting of metal of a metal-containing catalyst, an alkoxycarbonyl group derived from dialkyl carbonate or alkylaryl carbonate, an aryloxycarbonyl group derived from alkylaryl carbonate or diaryl carbonate and a carbonyl group derived from dialkyl carbonate, alkylaryl carbonate or diaryl carbonate

—(O)_(v)—Ar⁶—(OH)_(q-v)  (32)

(wherein Ar⁶ and q are as defined above, v is an integer of 1 to m, and an —OH group and an —O— group may be bonded to any position of the aromatic ring of Ar⁶ group).

Examples of Ar⁶ in the formulas (23) and (24) include aromatic groups represented by the following formulas (33), (34), (35), (36) and (37):

(wherein Y¹ is a single bond, a divalent alkylene group having 1 to 30 carbon atoms or a divalent group selected from —O—, —CO—, —S—, —SO₂—, —SO— and —COO—);

(wherein Y¹ is as defined above and each Y¹ may be the same or different); and

(wherein Z represents a trivalent group such as a trivalent alkanetriyl group having 1 to 30 carbon atoms and a trivalent aromatic group; at least one hydrogen atom on an aromatic ring may be substituted by another substituent such as a halogen atom, an alkoxy group having 1 to 30 carbon atoms, a phenyl group, a phenoxy group, a vinyl group, a cyano group, an ester group, an amide group or a nitro group).

Specific examples of aromatic polyhydroxy compounds described above include hydroquinone, resorcin, catechol, trihydroxybenzene (and isomers thereof), bis-(hydroxyphenyl)-propane (and isomers thereof), bis-(hydroxyphenyl)-methane (and isomers thereof), bis-(hydroxyphenyl)-ether (and isomers thereof), bis-(hydroxyphenyl)-ketone (and isomers thereof), bis-(hydroxyphenyl)-sulfone (and isomers thereof), bis-(hydroxyphenyl)-sulfide (and isomers thereof), dihydroxydiphenyl (and isomers thereof), bis-(dihydroxyphenyl)methane (and isomers thereof), 2-(hydroxyphenyl)-hydroxypropyl-phenol, dihydroxy-(hydroxyphenyldiphenyl) (and isomers thereof), tri-(hydroxyphenyl)ethane (and isomers thereof), tri-(hydroxyphenyl)-benzene (and isomers thereof), dihydroxynaphthalene (and isomers thereof) and trihydroxynaphthalene (and isomers thereof).

Of these aromatic polyhydroxy compounds and residues thereof, compounds that are often found in the process for producing the aromatic carbonate of the present invention need a careful attention. Examples of aromatic polyhydroxy compounds often found in the production process include the following (A), (B) and (C).

(A) oxidation product of aromatic monohydroxy compound which is a reactant (B) product produced by Fries rearrangement of diaryl carbonate obtained by the present reaction and oxidation product thereof (C) aromatic dihydroxy compound derived from phenol which is a reactant, represented by the following formula (38) and oxidation product thereof:

(wherein Y¹ is as defined above).

Examples of oxidation products (A) of an aromatic monohydroxy compound include compounds represented by the following formulas (39) and (40):

Examples of products (B) produced by Fries rearrangement of diaryl carbonate include compounds represented by the following formulas (41), (42) and (43).

Examples of oxidation products of the compound represented by the formula (41) include compounds represented by the formulas (44) and (45). Examples of oxidation products of the compounds represented by the formulas (42) and (43) include compounds represented by the formulas (46) and (47).

Examples of aromatic dihydroxy compounds (C) represented by the formula (38) include compounds represented by the formula (48).

Examples of oxidation products of the compound represented by the formula (48) include compounds represented by the formulas (49) and (50).

(wherein Y¹ is as defined above).

An aromatic polyhydroxy compound of type (A) is present in the production process because it is produced by oxidation of an aromatic monohydroxy compound due to mixing of a trace amount of oxygen to the system when producing aromatic carbonate, or because it is incorporated into the reaction system as impurities contained in the raw material aromatic monohydroxy compound. Typical examples of aromatic polyhydroxy compound (A) include dihydroxybenzene (and isomers thereof) and dihydroxydiphenyl (and isomers thereof).

A product produced by Fries rearrangement of diaryl carbonate of type (B) tends to be produced by a side reaction upon producing diaryl carbonate. Examples of polyhydroxy compounds (B) include 2,2′-dihydroxybenzophenone, 2,4′-dihydroxybenzophenone and 4,4′-dihydroxybenzophenone.

An aromatic dihydroxy compound of type (C) is a compound generally used as a monomer for producing aromatic polycarbonate. Aromatic polycarbonate can be produced by an transesterification of such aromatic dihydroxy compound and diaryl carbonate, and in the transesterification, an aromatic monohydroxy compound is produced as a by-product. The aromatic dihydroxy compound of type (C) is easily mixed to the production process when the by-product aromatic monohydroxy compound is to be used as a reactant in the present invention. Typical examples of such polyhydroxy compounds include 2,2-bis-(4-hydroxyphenyl)-propane.

The aromatic polyhydroxy compounds in the present invention also include an aromatic polyhydroxy compound described below, which is generally coexistent with 2,2-bis-(4-hydroxyphenyl)-propane:

The aromatic carboxyl compound categorized as a high boiling point material in the present invention is represented by the formula (51):

(wherein Ar⁷ is an aromatic group having a valence of r, r is an integer of 1 or more, s is an integer of 0 to r−1, and each —OH group and —(COOH) group may be bonded to any position of Ar⁷ group).

The residue of the aromatic carboxyl compound is represented by the formula (52) and is chemically bonded to at least one member selected from the group consisting of metal of a metal-containing catalyst, an alkoxycarbonyl group derived from dialkyl carbonate or alkylaryl carbonate, an aryloxycarbonyl group derived from alkylaryl carbonate or diaryl carbonate and a carbonyl group derived from dialkyl carbonate, alkylaryl carbonate or diaryl carbonate.

(wherein Ar⁷, r and s are as defined above, t is an integer of 0 to s, u is an integer of 0 to r−s, and —OH group, —(COOH) group, —O— group and —(COO)— group may be bonded to any position of Ar⁷).

The particular example of such aromatic carboxyl compounds and its residues include: aromatic carbonic acids such as benzoic acid, terephthalic acid, isophthalic acid, phthalic acid or the like; aromatic carbonates, such as methyl benzoate, phenyl benzoate, dimethyl terephtharate or the like; hydroxyl aromatic carbonic acids such as salicylic acid, p-hydroxybenzoic acid, m-hydroxybenzoic acid, dihydroxybenzoic acid (isomers thereof), carboxy diphenol (isomers thereof), 2-(4-hydroxyphenyl)-2-(3′-carboxy-4′-hydroxyphenyl)propane or the like; aryloxycarbonyl-(hydroxyl)-arenes such as phenyl salicylate, phenyl p-hydroxybenzoate, tolyl salicylate, tolyl p-hydroxybenzoate, phenyl dihydroxybenzoate (isomers thereof), tolyl dihydroxybenzoate (isomers thereof), phenoxycarbonyl diphenol (isomers thereof), 2-(4-hydroxyphenyl)-2-(3′-phenoxycarbonyl-4′-hydroxyphenyl)propane or the like; alkoxycarbonyl-(hydroxyl)-arenes such as methyl salicylate, methyl p-hydroxybenzoate, ethyl salicylate, ethyl p-hydroxybenzoate, methyl dihydroxybenzoate (isomers thereof), methoxycarbonyl diphenol (isomers thereof), 2-(4-hydroxyphenyl)-2-(3′-methoxycarbonyl-4′-hydroxyphenyl)propane or the like; aryloxycarbonyl-(alkoxy)-arenes such as phenyl methoxybenzoate (isomers thereof), tolyl methoxybenzoate (isomers thereof), phenyl ethoxybenzoate (isomers thereof), tolyl ethoxybenzoate (isomers thereof), phenyl hydroxyl-methoxybenzoate (isomers thereof), hydroxyl-methoxy-(phenoxycarbonyl)-diphenyl (isomers thereof), 2-(4-methoxyphenyl)-2-(3′-phenoxycarbonyl-4′-hydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(3′-phenoxycarbonyl-4′-methoxyphenyl)propane or the like; aryloxycarbonyl-(aryloxy)-arenes such as phenyl phenoxybenzoate (isomers thereof), tolyl phenoxybenzoate (isomers thereof), tolyl tolyloxybenzoate (isomers thereof), phenyl hydroxyl-phenoxy-benzoate (isomers thereof), hydroxyl-phenoxy-(phenoxycarbonyl)-diphenyl (isomers thereof), 2-(4-phenoxyphenyl)-2-(3′-phenoxycarbonyl-4′-hydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(3′-phenoxycarbonyl-4′-phenoxyphenyl)propane or the like; alkoxycarbonyl-(alkoxy)-arenes such as methyl methoxybenzoate (isomers thereof), ethyl methoxybenzoate (isomers thereof), methyl ethoxybenzoate (isomers thereof), ethyl ethoxybenzoate (isomers thereof), methyl hydroxyl-methoxybenzoate (isomers thereof), hydroxyl-methoxy-(methoxycarbonyl)-diphenyl (isomers thereof), 2-(4-methoxyphenyl)-2-(3′-methoxycarbonyl-4′-hydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(3′-methoxycarbonyl-4′-methoxyphenyl)propane or the like; alkoxycarbonyl-(aryloxy)-arenes such as methyl phenoxybenzoate (isomers thereof), ethyl phenoxybenzoate (isomers thereof), methyl tolyloxybenzoate (isomers thereof), ethyl tolyloxybenzoate (isomers thereof), phenyl hydroxyl-methoxy-benzoate (isomers thereof), hydroxyl-methoxy-(phenoxycarbonyl)-diphenyl (isomers thereof), 2-(4-methoxyphenyl)-2-(3′-phenoxycarbonyl-4′-hydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(3-phenoxycarbonyl-4′-methoxyphenyl)propane or the like; aryloxycarbonyl-(aryloxycarbonyloxy)-arenes such as phenyl phenoxycarbonyloxybenzoate (isomers thereof), tolyl phenoxycarbonyloxybenzoate (isomers thereof), tolyl tolyloxycarbonyloxybenzoate (isomers thereof), phenyl hydroxyl-phenoxycarbonyloxy-benzoate (isomers thereof), hydroxyl-phenoxycarbonyloxy-(phenoxycarbonyl)-diphenyl (isomers thereof), 2-[4-(phenoxycarbonyloxy)phenyl-2-(3′-phenoxycarbonyl-4′-hydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-[3′-phenoxycarbonyl-4′-(phenoxycarbonyloxy)phenyl]propane or the like; aryloxycarbonyl-(alkoxycarbonyloxy)-arenes such as phenyl methoxycarbonyloxybenzoate (isomers thereof), tolyl methoxycarbonyloxybenzoate (isomers thereof), phenyl ethoxycarbonyloxybenzoate (isomers thereof), tolyl ethoxycarbonyloxybenzoate (isomers thereof), phenyl hydroxyl-methoxycarbonyloxy-benzoate (isomers thereof), hydroxyl-methoxycarbonyloxy-(phenoxycarbonyl)-diphenyl (isomers thereof), 2-[4-(methoxycarbonyloxy)phenyl]-2-(3′-phenoxycarbonyl-4′-hydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-[3′-phenoxycarbonyl-4′-(methoxyccarbonyloxy)phenyl]propane or the like; alkoxycarbonyl-(aryloxycarbonyloxy)-arenes such as methyl phenoxycarbonyloxybenzoate (isomers thereof), ethyl phenoxycarbonyloxybenzoate (isomers thereof), methyl tolyloxycarbonyloxybenzoate (isomers thereof), ethyl tolyloxycarbonyloxybenzoate (isomers thereof), methyl hydroxyl-phenoxylcarbonyloxybenzoate (isomers thereof), hydroxyl-phenoxycarbonyloxy-(methoxycarbonyl)-diphenyl (isomers thereof), 2-[4-(phenoxycarbonyloxy)phenyl]-2-(3′-methoxycarbonyl-4′-hydroxyphenyl)propane, 2-(4-hydrorxyphenyl)-2-[3′-methoxycarbonyl-4′(phenoxycarbonyloxy)phenyl]propane or the like; alkoxycarbonyl-(alkoxycarbonyloxy)-arenes such as methyl methoxycarbonyloxybenzoate (isomers thereof), ethyl methoxycarbonyloxybenzoate (isomers thereof), methyl ethoxycarbonyloxybenzoate (isomers thereof), ethyl ethoxycarbonyloxybenzoate (isomers thereof), methyl hydroxyl-methoxycarbonyloxy-benzoate (isomers thereof), hydroxyl-methoxycarbonyloxy-(methoxycarbonyl)-diphenyl (isomers thereof), 2-[4-(methoxycarbonyloxy)phenyl]-2-(3′-methoxyarbonyl-4′-hydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-[3′-methoxycarbonyl-4′-(methoxycarbonyloxy)phenyl]propane or the like.

Among these aromatic carboxyl compounds and the residues thereof, the special attentions should be paid those tend to exist in the production process of aromatic carbonates of the present invention. Aromatic carboxyl compounds that tend to exist may include (D) and (E) described below.

(D) includes products of Fries rearrangement of aromatic carbonates which are obtained by the transesterification of the present invention, and hydrolysis products thereof. (E) includes products of Fries rearrangement of the transesterification products of the aromatic polyvalent hydroxyl compounds and hydrolysis products thereof.

As described earlier, in the production method of aromatic carbonates of the present invention, the reactions to obtain butyl phenyl carbonate and diphenyl carbonate from dibutylcarbonate and phenol are particularly important, and therefore, aromatic carboxyl compounds and residues thereof of (D) and (E) described above are shown below as examples.

Example of (D) may include: salicylic acid; p-hydroxybenzoic acid; phenyl salicylate; phenyl p-hydroxybenzoate, butyl salicylate; butyl p-hydroxybenzoate; phenyl butoxybenzoate (isomers thereof); phenyl phenoxybenzoate (isomers thereof); phenyl phenoxycarbonyloxybenzoate (isomers thereof); butyl phenoxycarbonyloxybenzoate (isomers thereof); butyl butoxycarbonyloxybenzoate (isomers thereof) or the like.

Example of (E) may include: dihydroxybenzoic acid (isomers thereof); phenyl dihydroxybenzoate (isomers thereof); phenoxycarbonyl diphenol (isomers thereof); 2-(4-hydroxyphenyl)-2-(3′-phenoxycarbonyl-4′-hydroxyphenyl)propane or the like.

Xanthones that are included in the high boiling point materials of the present invention include xanthone and the xanthone having at least one substituent on the aromatic ring selected from following various substituent group consisting of: alkyl groups such as a methyl group, ethyl group, propyl group, isopropyl group, butyl group, and isobutyl group; hydroxyl group; alkoxy groups such as a methoxy group, ethoxy group, propoxy group, isopropoxy group, and butoxy group; aryloxy groups such as a phenoxy group, tolyloxy group; alkoxycarbonyloxy groups such as a methoxycarbonyloxy group, ethoxycarbonyloxy group, propoxycarbonyloxy group, and buthoxycarbonyloxy group; aryloxycarbonyloxy groups such as a phenoxycarbonyloxy group, tolyroxycarbonyloxy group; a carboxyl group; alkoxycarbonyl groups such as a methoxycarbonyl group and ethoxycarbonyl group; aryloxycarbonyl groups such as a phenoxycarbonyl group and tolyloxycarbonyl group; and arylcarbonyloxy groups such as a benzoiloxy group and tolylcarbonyloxy group.

An active substance in the present invention is a substance that reacts with a high boiling point material and/or a metal-containing catalyst, and any substance may be used as long as a separable reaction mixture is produced as the result of the reaction. For example, the active substance includes an oxidizing agent, a reducing agent, a precipitating agent, an adsorption agent, a reactive solvent or the like. In particular, the oxidizing agent, precipitating agent, reactive solvent or the like are preferably used. These active substances may be used singly, or in combination of 2 kinds and further simultaneously or sequentially.

The product derived from the high boiling point substance in the present invention is the reaction products and/or un-reacted high boiling point substances that results from the reaction between the high boiling point substance and the active substance.

Also the product derived from the metal-containing catalyst is the reaction products and/or un-reacted metal-containing catalyst that results from the reaction between the metal-containing catalyst and the active substance.

The separation of the reaction mixture containing the product derived from the high boiling point substance and the product derived from the metal-containing catalyst may be carried out by any separation method as long as the method is able to separate this reaction mixture into two components, one that mainly contains the product derived from the high boiling point substance and the other that mainly contains the product derived from the metal-containing catalyst. For example, gas-condensation phase separation methods such as gas-liquid separation, gas-solid separation, gas-solid liquid phase separation or the like method; solid-liquid separation methods such as sedimentation, centrifugation, filtration or the like method; distillation method; extraction method; adsorption method; or the like may be used, and preferably, separation methods such as sedimentation, distillation, and adsorption are used. Further, these separation methods may be used singly, or in combination of the two or more methods simultaneously or sequentially.

The combination of this active substance and the separation method is not limited in particular, but the preferred methods for carrying out the present invention includes as follows.

(I) The gas-condensation phase separation method, wherein the active substance is an oxidizing agent, the reaction is an oxidizing reaction, the product derived from the high boiling point material are low boiling point oxidized products, and the product derived from the metal-containing catalyst is metallic oxide.

(II) The solid-liquid separation method, wherein the active substance is a precipitating agent, the reaction is the precipitating reaction, and the product derived from the metal-containing catalyst is the metal containing solid substance which presents in the reaction mixture.

(III) The distillation separation method, wherein the active substance is a reactive solvent, the reaction is the solvolysis, and the product derived from high boiling point material is one of the solvolysis with low boiling point.

On using the aforementioned method of (I), the oxidizing agent to be used is the one that oxidizes high boiling point material producing low boiling point oxidation products as the derivatives of the high boiling point material, and that oxidizes the metal-containing catalyst producing metallic oxide as the product derived from the metal-containing catalyst. Examples of those oxidizing agents include: air, molecular oxygen, ozone, hydrogen peroxide, silver oxide; organic peroxides such as peracetic acid, perbenzoic acid, benzoyl peroxide, tert-butylhydroperoxide, cumyl hydroperoxide or the like; oxo-acids such as nitrous acid, nitric acid, chloric acid, and hypochlorous acid and salts thereof or the like. Air, molecular oxygen, ozone, hydrogen peroxide, nitrous acid, and nitric acid are preferably used, and more preferably air and molecular oxygen are used.

The reaction between the liquid and an oxidizing agent is carried out in a phase selected from the group consists of liquid phase, gas-liquid mixed phase and gas-liquid solid mixed phase, although the reaction depends on the kind of the oxidizing agent and the reaction conditions. The reaction temperature, although it may be varied depending on the kind of oxidizing agent used, is normally −30-2000° C., preferably 0-1200° C. and more preferably 0-900° C. The reaction time, although it may be varied depending on the kind of the oxidizing agent and the reaction time, is normally 0.001-100 hours, preferably 0.1-20 hours. The reaction pressure is normally carried out under 10-10⁷ Pa, and preferably 10²-3×10⁶ Pa. This reaction may be carried out in a batch reaction or in continuous reaction.

In the method of the aforementioned (I), the separation of the reaction mixture is carried out by gas-condensation phase separation. The condensation phase means liquid phase, solid phase or mixed phase of solid and liquid. If the reaction mixture of the aforementioned oxidizing reaction is in liquid phase at the end of the oxidizing reaction, gas liquid mixed phase or gas liquid solid mixed phase, the condensed phase components consisting of mainly metal oxide may be obtained: by carrying out phase separation of the reaction mixture into the gas phase components consisting of mainly low boiling point products of oxidization and the condensation phase containing metal oxides; and by distilling or evaporating low boiling point oxidation products from the obtained condensation phase components.

If the metal-containing catalyst in the liquid is oxidized to metal oxide forming solid phase during the progression of the aforementioned oxidation reaction, the solid liquid mixture may be obtained while the reaction is in progress.

Further, the oxidation reaction mixture may be converted into solid phase only by evaporating the low boiling point oxidation product, which is produced by the oxidation of the high boiling point material, together with the volatile components in the liquid. This is the preferred method because, simultaneously with the oxidizing reaction, the solid phase which mainly consists of metal oxide is separated from the gas phase containing the low boiling point oxidation product.

The low boiling point oxidation product is a compound that is produced by the oxidation of a high boiling point material by the oxidizing agent, having a lower boiling point than that of the high boiling point material. The examples of the low boiling point oxidation product include carbon dioxide, water, carbon monoxide, organic compounds containing oxygen, unsaturated organic compounds, the high boiling point materials with reduced carbons or the like, although they may be varied depending on the kind of the oxidizing agent and high boiling point material used.

The metal oxide is the oxide of the metal in the metal-containing catalyst, and includes TiO, Ti₂O₃, TiO₂ or the like. When a metal-containing catalyst having a plurality of metals is used, a mixture of the corresponding metal oxides and/or the complex metal oxide is obtained.

In case the method of aforementioned (II) is used, this metal containing substance may be any metal containing substance as long as it exists as the solid in this reaction mixture and contains this metal. For example, it includes: a metal hydroxide; a metal chalcogenide such as metal oxide, a metal sulfide or the like; an inorganic acid salt such as metal carbonate, metal sulfate or the like; metal organic acid salt; metal complex; metal double salt or the like. Metal carbonates, metal hydroxides, metal oxides, metal sulfides and metal sulfates are preferable because their solubility in this reaction mixture is low. The reactive substance, starting material or the like may coordinate with these metal-containing substances.

Any precipitating agent may be used that reacts with the metal-containing catalyst producing the metal containing substance described above. For example, to precipitate these metal hydroxides, inorganic hydroxides such as alkali metal hydroxides, alkali earth metal hydroxide or the like, and water are used. In order to precipitate these metal oxides, inorganic oxides such as alkali metal oxides, alkali earth metal oxides or the like, and oxidizers such as hydrogen peroxide or the like are used. In order to precipitate these metal sulfides, inorganic sulfides such as alkali metal sulfide, alkali earth sulfide or the like, and hydrogen sulfide are used. In order to precipitate these metal carbonate, inorganic carbonate salts such as alkali metal carbonates, alkali earth metal carbonates or the like, and carbonic acid, carbon dioxide and water are used. In order to precipitate these metal sulfate, inorganic sulfate salts such as alkali metal sulfate, alkali earth metal salt or the like, sulfuric acid, sulfur trioxide and water are used.

The reaction between the metal-containing catalyst and the precipitating agent, although it may be varied depending on the kinds of the catalyst and the precipitating agent, and the reaction condition used, is normally carried out in the one phase condition selected from the group consisting of liquid phase, gas liquid mixed phase, gas liquid solid mixed phase and solid liquid mixed phase. The reaction temperature, although it may be varied depending on the kind of the precipitating agent used, is normally −70-600° C., preferably −30-400° C., more preferably −10-250° C.

The reaction time, although it may be varied depending on the kind of the precipitating agent and the reaction temperature, is normally 0.001-100 hour, preferably 0.1-20 hours. The reaction is usually carried out under the pressure of 10-10⁷ Pa. This reaction may be carried out as the batch or continuous reaction.

In the precipitating reaction, it is the preferable method to add a substance forming crystal nuclei. Further, although the metal containing substance exists as solid on separating this reaction mixture, it does not necessarily need to exist as solid while the precipitating reaction is proceeding, and it may be solidified through the operations such as cooling or the like after this reaction. In the case of the aforementioned (II), the separation of the reaction mixture is the solid-liquid separation, and the mixture is separated to a solid phase mainly consisting of the metal containing substance and a liquid phase mainly consisting of the product derived from the high boiling point material. For this solid liquid separation, normally sedimentation, centrifugation, filtration or the like separation method are used.

Further in carrying out the method of (II), the high boiling point material containing in the liquid may react or may not react in the precipitating reaction.

In case the method of the aforementioned (III) is used, the reactive solvent to be used may be any reactive solvent as long as it reacts with the high boiling point material and produces compounds with the boiling point lower than that of the high boiling point material. For example, water; lower alcohols such as methanol, ethanol, propanol (isomers thereof), butanol (isomers thereof), or the like; lower carboxylic acids such as formic acid, acetic acid, propionic acid or the like; carbonates such as dimethyl carbonate, diethyl carbonate, dibutyl carbonate or the like may be used. Water, methanol, ethanol, acetic acid, methyl acetate, ethyl acetate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate or the like are preferably used and more preferably, water is used.

The solvolysis in the present invention means the reaction between the reactive solvent and the high boiling point material, and the solvolysis products may undergo further reactions such as the decarboxylation reaction that is different from the solvolysis reaction. This low boiling point product of the solvolysis may be a product with a lower boiling point than the high boiling point material and its variety or structure may be varied depending upon the reactive solvent and the kind of the high boiling point material. The solvolysis products with low boiling point are explained particularly in following (i)-(iii), when the high boiling point material is phenyl salicylate that is one of aromatic carboxyl compounds.

(i) In the case where the reactive solvent is water: phenol and salicylic acid are produced by hydrolysis and this salicylic acid further undergoes decarboxylation reaction producing phenol and carbon dioxide.

(ii) In the case where the reactive solvent is alcohol: alkyl salicylate and phenol are produced by alcoholysis.

(iii) In the case where the reactive solvent is carboxylic acid: salicylic acid and phenyl carboxylate ester are produced by the transesterification and this salicylic acid further undergoes decarboxylation reaction converted into phenol and carbon dioxide.

Above explanation is based on the example of phenyl salicylate that is relatively simple structured aromatic carboxylic compound but similar reactions involving more complexed aromatic carboxylic compounds may also generate corresponding solvolysis products such as aromatic monohydroxy compound, ester of lower carboxylic acid and aromatic mono hydroxyl compound, ester of aromatic carboxyl compound and a lower alcohol, carbon dioxide or the like. In particular, aromatic monohydroxy compounds are preferable as solvolysis products because they are the reactive substances of the present invention and can be reused.

Since the liquid contains the metal-containing catalyst which normally functions as a catalyst for the solvolysis reaction, it is not necessary to use a catalyst for the solvolysis reaction in particular. However, the catalyst may be used for the purpose of improving the rate of reaction or the like.

The reaction between the high boiling point material and the reactive solvent is normally carried out, although it may be varied depending on the reaction condition, in one phase condition either liquid phase or solid liquid mixture phase.

The reaction temperature, although it may be varied depending on the kind of the reactive solvent used, is normally −30 to 400° C., preferably −10 to 300° C., more preferably −0 to 250° C.

The reaction time, although it may be varied depending on the kind of the reactive solvent and the reaction temperature, normally 0.001-100 hour, preferably 0.1-20 hours. The reaction is usually carried out under the pressure of 10-10⁷ Pa. This reaction may be carried out as the batch or continuous reaction.

The metal-containing catalyst may or may not catalyze the solvolysis reaction. In case of reacting water or alcohols as the reactive solvent to the liquid containing an aromatic carboxylic compound as the high boiling point material, carbon dioxide is generated as one of the derivations from the high boiling point material due to the decarboxylation. Thus this carbon dioxide acts as the precipitating agent and reacts with the metal-containing catalyst, and metal containing substances such as metal carbonate or the like may be obtained in soluble and/or solidified states.

In the method of the aforementioned (III), the reaction mixture is separated by distillation, and the low boiling points solvolysis products that are the products derived from the high boiling point material are mainly obtained as distillates. The metal-containing catalyst remains in the residual liquid in the distillation still. This distillation separation is carried out at the temperature normally 10-300° C., preferably 50-250° C., represented as the temperature of the liquid in the distillation still. The reaction is usually carried out under the pressure of 0.1-1.0×10⁶ Pa, preferably 1.0-1.0×10⁵ Pa. The distillation may be carried out batch-wise or continuously.

When the products derived from the metal-containing catalyst, which are obtained by separating the reaction mixture of the liquid from the active substance, are to be recycled in the system, the composition containing the products derived from the metal-containing catalyst, which are obtained by separation of the reaction mixture, in liquid, solid or liquid solid mixed phase may be recycled into the system as they are, or if this composition contains other components than the products derived from the metal-containing catalyst, a part or the whole components may be separated and then recycled in the system. Further, the reaction solution or slurry, which is obtained by reacting the products derived from the metal-containing catalyst to the starting material or to the reactive substance, may be recycled. This method is the preferred method when the products derived from the metal-containing catalyst are in a solid or a solid liquid mixed phase.

Concerning the high boiling point liquid materials to be removed from the system, those concentrations which may be varied depending on the kind of materials, are not preferred to be kept extremely low because the volume of the liquid, which is subjected to the removal, becomes too large. Also, if the concentration of the high boiling point material is too high, handling becomes difficult due to the increase of the boiling point and the viscosity. Therefore, the concentration of the high boiling point material in the liquid, which is subjected to the removal, is normally 0.01-99% by weight, preferably 0.1-95% by weight and more preferably 1-90% by weight.

Further, when the high boiling point material is an aromatic polyvalent hydroxyl compound, the weight ratio of aromatic polyvalent hydroxyl compound to the metal of the catalyst in the liquid is normally kept at 2 or below to prevent deposition and attachment of the catalyst in the reactor and the lines.

By using the metal-containing catalyst of the present invention, factors that rendered the production unstable in the past such as clogging of the distillation column, deposition of the catalyst component to the wall are surprisingly improved.

Further, the preferred example of the present invention includes the usage of diaryl carbonate, purified by the method of the present invention, in aromatic polycarbonate production by the transesterification method. Polycarbonate which is produced by the transesterification method, depending on the polymerization method, tends to show red coloring due to the metal content in the catalyst for diphenyl carbonate which is used as the material, especially when the Ti content is greater than 1 ppm. However, the aromatic carbonate, particularly important diphenyl carbonate, which is produced by the method of the present invention contains Ti at 1 ppm or below. Polycarbonate is easily produced by the transesterification polymerization with bisphenol A. Thus polycarbonate produce in the present invention is high quality because it contains less Ti which causes coloring of polycarbonate.

Further, in producing aromatic polycarbonate by the transesterification method, the polymerization at high rate may be achieved using the diaryl carbonate produced by the method of the present invention. Still further, aromatic polycarbonate produced by the transesterification method, which is obtained using aromatic dihydroxy compound and diaryl carbonate produced by the method of the present invention, has no coloring and is high quality.

EFFECT OF THE INVENTION

According to the present invention, high purity diaryl carbonate that is easily separated from a catalyst is produced, wherein a starting material selected from the group consisting of a dialkyl carbonate, an alkylaryl carbonate and a mixture thereof and a reactive substance selected from the group consisting of an aromatic monohydroxy compound, an alkylaryl carbonate and a mixture thereof are reacted in the presence of a metal-containing catalyst to produce aromatic carbonates while by-products alcohols and/or dialkyl carbonates are distilled out of the system.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a process flow chart related to the production of aromatic carbonate in the present invention; and

FIG. 2 is a process flow chart related to the purification of diaryl carbonate in the present invention.

FIG. 3 is a process flow chart related to the structure of aromatic carbonic acid ester.

FIG. 4 is a process flow chart related to the structure of aromatic carbonic acid ester.

DESCRIPTION OF SYMBOLS

-   1, 4, 7, 10, 13, 16, 19, 22, 25, 28, 31, 34, 37, 40, 43, 46, 54, 57,     58, 60: line -   50, 56: inlet line -   2, 14, 26, 38, 51: preheater -   3, 15, 27, 39, 49: continuous multi-stage distillation column -   5, 17, 29, 41: cooler -   55: condenser -   6, 18, 30, 42: gas liquid separator -   11, 23, 35, 47, 59: reboiler -   8, 12, 20, 24, 33, 36, 44, 48: storage tank -   9, 21, 32, 45: pressure control valve -   52: top of the column -   53: bottom of the column

BEST MODE FOR CARRYING OUT THE INVENTION

Next, the present invention will be explained in particular by the examples, but the present invention is not limited by these examples. Further, the measurements for the concentration of the catalyst and the concentration of the metal derived from the metal-containing catalyst in aromatic carbonate were carried out using an ICP/AES (Inductively Coupled Plasma/Atomic Emission Spectroscopy: Detection limit of 0.1 ppm). The concentrations of the organic components in the liquid were measured by Gas Chromatography.

(1) Conditions for Gas Chromatographic Analysis.

Column: DB-1 (J & W Scientific)

Liquid phase: 100% dimethylpolysiloxane

Length: 30 m

Internal diameter: 0.25 mm

Film thickness: 1 μm

Column temperature: 50° C. (increased by 10° C./min) 300° C.

Injection temperature: 300° C.

Detector temperature: 300° C.

Detection method: FID

(2) Quantitative Analysis

The analysis sample solutions are quantitatively analyzed based on the standard curves prepared by carrying out the analyses on the calibration samples of each standard substance.

(3) Confirmation of Ti—O—Ti Bond.

The presence of Ti—O—Ti bond is estimated by identifying Ti substituent (or ligand) from the result of ¹H-NMR, and subtracting the oxygen value derived from this substituent (or ligand) from the result of the element analysis (C, H, O, Ti) and by assuming this oxygen value as the cross linkage oxygen derived from Ti—O—Ti.

(4) Conditions for NMR analysis

Device: JNM-A400 FT-NMR system made by JEOL Ltd.

(Preparation of Samples for ¹H-NMR, ¹³C-NMR Analysis)

The metal-containing catalyst was weighed in the range of 0.1 g-1 g and mixed homogeneously with deuterated chloroform (Aldrich Co. 99.8%) or carbon tetrachloride that weighed in the range of 0.05 g-0.7 g to prepare samples for the NMR analysis. TMS (tetramethyl silane) was used as the internal standard.

EXAMPLES

The present invention will be described based on the examples.

Example 1 Production of Aromatic Carbonic Acid Ester

Aromatic carbonate was produced using a device shown in FIG. 1. The reaction was carried out by supplying continuously at a rate of about 109 g/Hr, through a preheater 2 and a line 1, a mixed solution consisting of dibutyl carbonate, phenol and, as the catalyst, phenyl titanate dimer.2PhOH adduct [(PhO)₃—Ti—O—Ti—(OPh)₃.2PhOH] (result of element analysis: C=67.2, H=4.93, O=16.77, Ti=11.1; result of ¹H-NMR analysis: PhOH and PhO groups exist at the ratio of 2:6. In one molecule, two Ti atoms and one oxygen atom that is not derived from PhOH and PhO groups exist, that is, one Ti—O—Ti bond exists; molecular weight without the adduct PhOH: 670; vapor pressure: 1 Pa or below at 230° C.) (the mixed solution in which that the ratio by weight of dibutyl carbonate to phenol was adjusted to about 65/35, and Ti as atoms was adjusted to about 10,000 ppm of the whole liquid) from the middle stage of a continuous multi-stage distillation column 3, which was composed of a condensation part, which was 2 inch in the internal diameter, 0.5 m in the column length and filled with 10 stages of sieve trays, and a recovery part which was 2 inch in the internal diameter, 1 m in the column length and filled with Dixon packing (6 mmφ). The condensation part was disposed in the lower part of the stage where the mixture was supplied continuously, and the recovery part was disposed in the upper part. The heat required for the reaction and distillation was supplied by circulating the liquid in the lower part of the column through a line 10 and a reboiler 11, and the temperature at the bottom of the multi-stage distillation column was controlled to be about 230° C. The reaction liquid was continuously removed from the bottom of the continuous multi-stage distillation column 3 through a line 10 to a storage tank 12 at 90 g/Hr. The catalyst was dissolved in the reaction liquid.

After the low boiling point liquid mixture containing 1-butanol as a by-product was removed from the top of the column through a line 4, and then it was liquefied by a cooler 5, and a part of it was removed continuously to a storage tank 8 at 19 g/Hr and the rest was refluxed to the distillation column (reflux ratio=1.9).

The liquid removed to the storage tank 12 was composed of about 23% by weight of phenol, about 56% by weight dibutyl carbonate, about 12% by weight of butyl phenyl carbonate, about 0.2% by weight of diphenyl carbonate, about 0.3% by weight of 1-butanol and the catalyst. The liquid removed to the storage tank 8 was composed of about 99% by weight of 1-butanol, about 0.5% by weight of phenol, and about 0.2% by weight of dibutyl carbonate.

After the reaction in the continuous multi-stage distillation column 3, the reaction was carried out using a continuous multi-stage distillation column 15. The continuous multi-stage distillation column 15, as in the case of the continuous multi-stage distillation column 3, was composed of a condensation part, which is 2 inch in the internal diameter, 0.5 m in the column length and filled with 10 stages of sieve trays, and a recovery part which is 2 inch in the internal diameter, 1 m in the column length and filled with Dixon packing (6 mmφ), and the condensation part was disposed in the lower part of the stage where the reaction liquid containing the catalyst was supplied continuously from the storage tank 12 to this distillation column 15, and the recovery part was disposed in the upper part.

The reaction was carried out by supplying continuously through a line 13 the reaction liquid, which was removed from the bottom of the continuous multi-stage distillation column 3 through the line 10 to the storage tank 12, to the continuous multi-stage distillation column 15 at 100 g/Hr after preheating with a preheater 14. The heat required for the reaction and distillation was supplied by circulating the liquid in the lower part of the column through a line 22 and a reboiler 24, and the temperature at the bottom of the multi-stage distillation column is controlled to be about 220° C.

The reaction liquid was continuously removed from the bottom of the continuous multi-stage distillation column 15 through the line 22 to a storage tank 24 at 17 g/Hr. After the low boiling point liquid mixture containing dibutylcarbonate as a by-product was removed from the top of the column through a line 16, and then it was liquefied by a cooler 17, and a part of it was removed continuously to a storage tank 20 at 83 g/Hr and the rest was refluxed to the distillation column (reflux ratio=4).

The liquid removed to the storage tank 24 was composed of about 5% by weight of dibutyl carbonate, about 74% by weight of butyl phenyl carbonate, about 10% by weight of diphenyl carbonate, and the catalyst. The liquid removed to the storage tank 20 was composed of about 0.3% by weight of 1-butanol, about 18% by weight of phenol, and about 81% by weight of dibutyl carbonate. No deposit or the like were found in the distillation column on inspection.

[Purification of Diaryl Carbonate]

Purification of diaryl carbonate was carried out with a device shown in FIG. 2. The distillation separation was carried out by continuously feeding the liquid, which was removed to the storage tank 24, through a line 25 passing a preheater 26 at about 192 g/Hr to about 0.1 m above the middle stage of a continuous multi-stage distillation column 27, which was a column filled with Dixon packing (6 mmφ) with an internal diameter of 2 inch and a length of 1 m.

The heat required for the distillation separation was supplied by circulating the liquid in the lower part of the column through a line 34 and a reboiler 35, and the temperature at the bottom of the multi-stage distillation column is controlled to be about 210° C. The bottom liquid was continuously removed from the bottom of the continuous multi-stage distillation column 27 through the line 34 to the storage tank 36 at about 90 g/Hr. After removing from the top of the column through the line 28, the distillate was liquefied by a cooler 29 and was removed continuously to a storage tank 33 at about 102 g/Hr. The liquid removed to the storage tank 33 is composed of dibutyl carbonate: about 0.6% by weight, butyl phenyl carbonate: about 73% by weight, diphenyl carbonate: about 26% by weight.

The distillation separation was carried out by continuously feeding the liquid, which was continuously removed to the storage tank 33, through a line 37 passing a preheater 38 at about 101 g/Hr to the middle stage of a continuous multi-stage distillation column 39, which was a column filled with Dixon packing (6 mmφ) with an internal diameter of 2 inch and a length of 2 m. The heat required for the distillation separation was supplied by circulating the liquid in the lower part of the column through a line 46 and a reboiler 47, and the temperature at the bottom of the multi-stage distillation column was controlled to be about 200° C. The bottom liquid was continuously removed from the bottom of the continuous multi-stage distillation column 39 through the line 46 to a storage tank 48 at about 19 g/Hr.

After removing from the top of the column through a line 40, the distillate was liquefied by a cooler 41 and was removed continuously to a storage tank 44 at about 82 g/Hr. The liquid removed to the storage tank 44 is composed of dibutyl carbonate: about 0.7% by weight, butyl phenyl carbonate: about 90% by weight, diphenyl carbonate: about 9% by weight.

White liquid that was solidified at ambient temperature was continuously removed to a storage tank 48 and contained diphenyl carbonate: about 100% by weight, and butyl phenyl carbonate was below the detection limit. The analysis of the liquid indicated that Ti was below the detection limit. Inspection of the distillation column revealed not deposit or the like.

Comparative Example 1 Production of Aromatic Carbonate

Aromatic carbonate was produced in the device shown in FIG. 1. The reaction was carried out by supplying continuously at a rate of about 109 g/Hr, through a preheater 2 and a transport line 1, a mixed solution consisting of dibutyl carbonate, phenol, and phenyl titanate [Ti(OPh)₄] (this phenyl titanate: adduct with phenol; molecular weight without the adduct phenol: 420; vapor pressure: about 15 Pa at 230° C.) (the mixed solution in which the ratio by weight of dibutyl carbonate to phenol was adjusted to about 65/35, and Ti as atoms was adjusted to about 10,000 ppm of the whole liquid) from the middle stage of a continuous multi-stage distillation column 3, which is composed of a condensation part, which is 2 inch in the internal diameter, 0.5 m in the column length and filled with 10 stages of sieve trays, and a recovery part which is 2 inch in the internal diameter, 1 m in the column length and filled with Dixon packing (6 mmφ). The condensation part was disposed in the lower part of the stage where the mixture was supplied continuously, and the recovery part was disposed in the upper part.

The heat required for the reaction and distillation was supplied by circulating the liquid in the lower part of the column through a line 10 and a reboiler 11, and the temperature at the bottom of the multi-stage distillation column is controlled to be about 230° C. The reaction liquid was continuously removed from the bottom of the continuous multi-stage distillation column 3 through the line 10 to a storage tank 12 at 90 g/Hr.

After the low boiling point liquid mixture containing 1-butanol as a by-product was removed from the top of the column through a line 4, and then it was liquefied by the cooler 5, and a part of it was removed continuously to a storage tank 8 at 19 g/Hr and the rest was refluxed to the distillation column (reflux ratio=1.9). The liquid removed to the storage tank 12 was composed of: phenol: about 23% by weight, dibutyl carbonate: about 56% by weight, butyl phenyl carbonate: about 12% by weight, diphenyl carbonate: about 0.2% by weight, 1-butanol: about 0.3% by weight. The liquid removed to the storage tank 8 was composed of 1-butanol: about 99% by weight, phenol: about 0.5% by weight, and dibutyl carbonate: about 0.2% by weight.

After the reaction in the continuous multi-stage distillation column 3, the reaction was carried out using a continuous multi-stage distillation column 15. The continuous multi-stage distillation column 15, like the continuous multi-stage distillation column 3, is composed of a condensation part, which is 2 inch in the internal diameter, 0.5 m in the column length and filled with 10 stages of sieve trays, and a recovery part which is 2 inch in the internal diameter, 1 m in the column length and filled with Dixon packing (6 mmφ), and the condensation part was disposed in the lower part of the stage where the reaction liquid containing the catalyst was supplied continuously from the storage tank 12 to this distillation column 15, and the recovery part was disposed in the upper part.

The reaction was carried out by supplying continuously through a line 13 the reaction liquid, which was removed from the bottom of the continuous multi-stage distillation column 3 through the line 10 to the storage tank 12, to the continuous multi-stage distillation column 15 at 100 g/Hr after preheating with a preheater 14. The heat required for the reaction and distillation was supplied by circulating the liquid in the lower part of the column through a line 22 and a reboiler 24, and the temperature at the bottom of the multi-stage distillation column is controlled to be about 220° C.

The reaction liquid was continuously removed from the bottom of the continuous multi-stage distillation column 15 through the line 22 to a storage tank 24 at 17 g/Hr. After the low boiling point liquid mixture containing dibutylcarbonate as a by-product was removed from the top of the column through a line 16, and then it was liquefied by a cooler 17, and a part of it was removed continuously to a storage tank 20 at 83 g/Hr and the rest was refluxed to the distillation column (reflux ratio=4).

The liquid removed to the storage tank 24 was composed of dibutyl carbonate: about 5% by weight, butyl phenyl carbonate: about 74% by weight, diphenyl carbonate: about 10% by weight. The liquid removed to the storage tank 20 was composed of about 1-butanol: 0.3% by weight, phenol: about 18% by weight, and dibutyl carbonate: about 81% by weight.

[Purification of Diaryl Carbonate]

Purification of diaryl carbonate was carried out with a device shown in FIG. 2. The distillation separation was carried out by continuously feeding the liquid, which was removed to the storage tank 24, through a line 25 passing a preheater 26 at about 100 g/Hr to about 0.1 m above the middle stage of a continuous multi-stage distillation column 27, which was a column filled with Dixon packing (6 mmφ) with an internal diameter of 2 inch and a length of 1 m.

The heat required for the distillation separation was supplied by circulating the liquid in the lower part of the column through a line 34 and a reboiler 35, and the temperature at the bottom of the multi-stage distillation column was controlled to be about 210° C. The bottom liquid was continuously removed from the bottom of the continuous multi-stage distillation column 27 through the line 34 to the storage tank 36 at about 20 g/Hr.

After removing from the top of the column through the line 28, the distillate was liquefied by the cooler 29 and was removed continuously to a storage tank 33 at about 80 g/Hr.

The liquid removed to the storage tank 33 is composed of dibutyl carbonate: about 6% by weight, butyl phenyl carbonate: about 86% by weight, diphenyl carbonate: about 7.5% by weight.

The distillation separation was carried out by continuously feeding the liquid, which was continuously removed to the storage tank 33, through a line 37 passing a preheater 38 at about 100 g/Hr to the middle stage of a continuous multi-stage distillation column 39, which was a column filled with Dixon packing (6 mmφ) with an internal diameter of 2 inch and a length of 2 m. The heat required for the distillation separation was supplied by circulating the liquid in the lower part of the column through the line 46 and reboiler 47, and the temperature at the bottom of the multi-stage distillation column is controlled to be about 230° C.

The bottom liquid was continuously removed from the bottom of the continuous multi-stage distillation column 39 through a line 46 to a storage tank 48 at about 8 g/Hr. After removing from the top of the column through the line 40, the distillate was liquefied by a cooler 41 and was removed continuously to a storage tank 44 at about 92 g/Hr.

The liquid removed to the storage tank 44 is composed of dibutyl carbonate: about 6% by weight, butyl phenyl carbonate: about 94% by weight.

The liquid removed to a storage tank 48 was solid at ambient temperature but had a coloring of red. The analysis of the liquid indicated that Ti content of about 5 ppm.

Example 2 Production of Aromatic Carbonate

Aromatic carbonate was produced using a device shown in FIG. 1. The reaction was carried out by supplying continuously at a rate of about 100 g/Hr, through the preheater 2 and the transport line 1, a mixed solution consisting of dibutyl carbonate, phenol and, as a catalyst, di(phenyl salicylate) titanate-diphenolate (molecular weight: 660, vapor pressure: 1 Pa or below at 230° C.) (the mixed solution in which the ratio by weight of dibutyl carbonate an phenol was adjusted to about 65/35, and Ti as atoms was adjusted to about 10,000 ppm of the whole liquid) from the middle stage of a continuous multi-stage distillation column 3, which is composed of the condensation part, which is 2 inch in the internal diameter, 0.5 m in the column length and filled with 10 stages of sieve trays, and the recovery part which is 2 inch in the internal diameter, 1 m in the column length and filled with Dixon packing (6 mmφ).

The condensation part was disposed in the lower part of the stage where the mixture liquid was supplied continuously, and the recovery part was disposed in the upper part. The heat required for the reaction and distillation was supplied by circulating the liquid in the lower part of the column through a line 10 and a reboiler 11, and the temperature at the bottom of the multi-stage distillation column is controlled to be about 230° C.

The reaction liquid was continuously removed from the bottom of the continuous multi-stage distillation column 3 through the line 10 to a storage tank 12 at 95 g/Hr. The catalyst was dissolved in the reaction liquid.

After the low boiling point liquid mixture containing 1-butanol as a by-product was removed from the top of the column through a line 4, and then it was liquefied by the cooler 5, and a part of it was removed continuously to a storage tank 8 at 5 g/Hr and the rest was refluxed to the distillation column (reflux ratio=2).

The liquid removed to the storage tank 12 was composed of phenol: about 26% by weight, dibutyl carbonate: about 50% by weight, butyl phenyl carbonate: about 12% by weight, diphenyl carbonate: about 0.2% by weight, 1-butanol: about 0.6% by weight and the catalyst. The liquid removed to the storage tank 8 was composed of 1-butanol: about 90% by weight, phenol: about 7% by weight, and dibutyl carbonate: about 3% by weight.

After the reaction in the continuous multi-stage distillation column 3, the reaction was carried out using a continuous multi-stage distillation column 15. The continuous multi-stage distillation column 15, as in the case of the continuous multi-stage distillation column 3, was composed of a condensation part, which is 2 inch in the internal diameter, 0.5 m in the column length and filled with 10 stages of sieve trays, and the recovery part which is 2 inch in the internal diameter, 1 m in the column length and filled with Dixon packing (6 mmφ), and the condensation part was disposed in the lower part of the stage where the reaction liquid containing the catalyst was supplied continuously from the storage tank 12 to this distillation column 15, and the recovery part was disposed in the upper part.

The reaction was carried out by supplying continuously through a line 13 the reaction liquid, which was removed from the bottom of the continuous multi-stage distillation column 3 through the line 10 to the storage tank 12, to the continuous multi-stage distillation column 15 at 95 g/Hr after preheating with a preheater 14. The heat required for the reaction and distillation was supplied by circulating the liquid in the lower part of the column through a line 22 and a reboiler 24, and the temperature at the bottom of the multi-stage distillation column was controlled to be about 220° C.

The reaction liquid was continuously removed from the bottom of the continuous multi-stage distillation column 15 through the line 22 to a storage tank 24 at about 19 g/Hr. After the low boiling point liquid mixture containing dibutylcarbonate as a by-product was removed from the top of the column through a line 16, and then it was liquefied by a cooler 17, and a part of it was removed continuously to a storage tank 20 at 76 g/Hr and the rest was refluxed to the distillation column (reflux ratio=4).

The liquid removed to the storage tank 24 was composed of dibutyl carbonate: about 0.3% by weight, butyl phenyl carbonate: about 38% by weight, diphenyl carbonate: about 14% by weight and also the catalyst. The liquid removed to the storage tank 20 was composed of 1-butanol: about 0.7% by weight, phenol: about 33% by weight, and dibutyl carbonate: about 65% by weight, butyl phenyl carbonate: about 1% by weight. No deposit or the like were found in the distillation column on inspection.

[Purification of Diaryl Carbonate]

Purification of diaryl carbonate was carried out with a device shown in FIG. 2. The distillation separation was carried out by continuously feeding the liquid, which was removed to the storage tank 24, through a line 25 passing a preheater 26 at about 192 g/Hr to about 0.1 m above the middle stage of a continuous multi-stage distillation column 27, which was a column filled with Dixon packing (6 mmφ) with an internal diameter of 2 inch and a length of 1 m.

The heat required for the distillation separation was supplied by circulating the liquid in the lower part of the column through a line 34 and a reboiler 35, and the temperature at the bottom of the multi-stage distillation column is controlled to be about 210° C. The bottom liquid was continuously removed from the bottom of the continuous multi-stage distillation column 27 through the line 34 to the storage tank 36 at about 90 g/Hr.

After removing from the top of the column through the line 28, the distillate was liquefied by a cooler 29 and was removed continuously to a storage tank 33 at about 102 g/Hr. The liquid removed to the storage tank 33 is composed of dibutyl carbonate: about 0.6% by weight, butyl phenyl carbonate: about 73% by weight, diphenyl carbonate: about 26% by weight.

The distillation separation was carried out by continuously feeding the liquid, which was continuously removed to the storage tank 33, through a line 37 passing a preheater 38 at about 101 g/Hr to the middle stage of a continuous multi-stage distillation column 39, which was a column filled with Dixon packing (6 mmφ) with an internal diameter of 2 inch and a length of 2 m. The heat required for the distillation separation was supplied by circulating the liquid in the lower part of the column through a line 46 and a reboiler 47, and the temperature at the bottom of the multi-stage distillation column was controlled to be about 200° C.

The bottom liquid was continuously removed from the bottom of the continuous multi-stage distillation column 39 through the line 46 to a storage tank 48 at about 19 g/Hr. After removing from the top of the column through a line 40, the distillate was liquefied by a cooler 41 and was removed continuously to the storage tank 44 at about 82 g/Hr.

The liquid removed to the storage tank 44 is composed of dibutyl carbonate: about 0.7% by weight, butyl phenyl carbonate: about 90% by weight, diphenyl carbonate: about 9% by weight. White liquid that was solidified at ambient temperature was continuously removed to a storage tank 48 and contained diphenyl carbonate: about 100% by weight, and butyl phenyl carbonate was below the detection limit. The analysis of the liquid indicated that Ti content was about 0.8 ppm. Inspection of the distillation column revealed no deposit or the like.

Example 3 Production of Aromatic Carbonate

Aromatic carbonate was produced using a device shown in FIG. 1. The reaction was carried out by supplying continuously at a rate of about 109 g/Hr, through the preheater 2 and the line 1, a mixed solution consisting of dibutyl carbonate, phenol and, as a catalyst, butyl titanate trimer [(BuO)₃—Ti—O—Ti—(OBu)₂—O—Ti—(OBu)₃] (result of element analysis: C=50.5, H=9.5, O=21.1, Ti=18.9; since oxygen derived from BuO is 16.8, the number of bridging oxygen is 2, that is, there are two Ti—O—Ti bonds; molecular weight: 760; vapor pressure: 1 Pa or below at 230° C.) (the mixed solution in which the ratio by weight of dibutyl carbonate to phenol was adjusted to about 65/35, and Ti as atoms was adjusted to about 10,000 ppm of the whole liquid, and this catalyst was dissolved in this mixture) from the middle stage of a continuous multi-stage distillation column 3, which was composed of a condensation part, which was 2 inch in the internal diameter, 0.5 m in the column length and filled with 10 stages of sieve trays, and a recovery part which was 2 inch in the internal diameter, 1 m in the column length and filled with Dixon packing (6 mmφ).

The condensation part was disposed in the lower part of the stage where the mixture liquid was supplied continuously, and the recovery part was disposed in the upper part. The heat required for the reaction and distillation was supplied by circulating the liquid in the lower part of the column through a line 10 and a reboiler 11, and the temperature at the bottom of the multi-stage distillation column was controlled to be about 230° C.

The reaction liquid was continuously removed from the bottom of the continuous multi-stage distillation column 3 through the line 10 to a storage tank 12 at 90 g/Hr. The catalyst was dissolved in the reaction liquid.

After the low boiling point liquid mixture containing 1-butanol as a by-product was removed from the top of the column through a line 4, and then it was liquefied by the cooler 5, and a part of it was removed continuously to the storage tank 8 at 19 g/Hr and the rest was refluxed to the distillation column (reflux ratio=1.9). The liquid removed to the storage tank 12 was composed of phenol: about 23% by weight, dibutyl carbonate: about 56% by weight, butyl phenyl carbonate: about 12% by weight, diphenyl carbonate: about 0.2% by weight, 1-butanol: about 0.3% by weight and also the catalyst. The liquid removed to the storage tank 8 was composed of 1-butanol: about 99% by weight, phenol: about 0.5% by weight, and dibutyl carbonate: about 0.2% by weight.

After the reaction in the continuous multi-stage distillation column 3, the reaction was carried out using a continuous multi-stage distillation column 15. The continuous multi-stage distillation column 15, as in the case of the continuous multi-stage distillation column 3, was composed of a condensation part, which is 2 inch in the internal diameter, 0.5 m in the column length and filled with 10 stages of sieve trays, and a recovery part which is 2 inch in the internal diameter, 1 m in the column length and filled with Dixon packing (6 mmφ), and the condensation part was disposed in the lower part of the stage where the reaction liquid containing the catalyst was supplied continuously from the storage tank 12 to this distillation column 15, and the recovery part was disposed in the upper part.

The reaction was carried out by continuously supplying through a line 13 the reaction liquid, which was removed from the bottom of the continuous multi-stage distillation column 3 through the line 10 to the storage tank 12, to the continuous multi-stage distillation column 15 at 100 g/Hr after preheating with a preheater 14. The heat required for the reaction and distillation was supplied by circulating the liquid in the lower part of the column through a line 22 and a reboiler 24, and the temperature at the bottom of the multi-stage distillation column was controlled to be about 220° C.

The reaction liquid was continuously removed from the bottom of the continuous multi-stage distillation column 15 through the line 22 to a storage tank 24 at 17 g/Hr. After the low boiling point liquid mixture containing dibutylcarbonate as a by-product was removed from the top of the column through a line 16, and then it was liquefied by a cooler 17, and a part of it was removed continuously to a storage tank 20 at 83 g/Hr and the rest was refluxed to the distillation column (reflux ratio=4).

The liquid removed to the storage tank 24 was composed of dibutyl carbonate: about 5% by weight, butyl phenyl carbonate: about 74% by weight, diphenyl carbonate: about 10% by weight and also the catalyst. The liquid removed to the storage tank 20 was composed of 1-butanol: about 0.3% by weight, phenol: about 18% by weight, and dibutyl carbonate: about 81% by weight. No deposit or the like were found in the distillation column on inspection.

[Purification of Diaryl Carbonate]

Purification of diaryl carbonate was carried out with the device shown in FIG. 2. The distillation separation was carried out by continuously feeding the liquid, which was removed to the storage tank 24, through a line 25 passing a preheater 26 at about 192 g/Hr to about 0.1 m above the middle stage of a continuous multi-stage distillation column 27, which was a column filled with Dixon packing (6 mmφ) with an internal diameter of 2 inch and a length of 1 m. The heat required for the distillation separation was supplied by circulating the liquid in the lower part of the column through a line 34 and a reboiler 35, and the temperature at the bottom of the multi-stage distillation column is controlled to be about 210° C. The bottom liquid was continuously removed from the bottom of the continuous multi-stage distillation column 27 through the line 34 to the storage tank 36 at about 90 g/Hr. After removing from the top of the column through the line 28, the distillate was liquefied by a cooler 29 and was removed continuously to a storage tank 33 at about 102 g/Hr.

The liquid removed to the storage tank 33 is composed of dibutyl carbonate: about 0.6% by weight, butyl phenyl carbonate: about 73% by weight, diphenyl carbonate: about 26% by weight.

The distillation separation was carried out by continuously feeding the liquid, which was continuously removed to the storage tank 33, through the line 37 passing a preheater 38 at about 101 g/Hr to the middle stage of the continuous multi-stage distillation column 39, which was a column filled with Dixon packing (6 mmφ) with an internal diameter of 2 inch and a length of 2 m. The heat required for the distillation separation was supplied by circulating the liquid in the lower part of the column through the line 46 and reboiler 47, and the temperature at the bottom of the multi-stage distillation column is controlled to be about 200° C.

The bottom liquid was continuously removed from the bottom of the continuous multi-stage distillation column 39 through the line 46 to the storage tank 48 at about 19 g/Hr.

After removing from the top of the column through the line 40, the distillate was liquefied by the cooler 41 and was removed continuously to the storage tank 44 at about 82 g/Hr. The liquid removed to the storage tank 44 is composed of dibutyl carbonate: about 0.7% by weight, butyl phenyl carbonate: about 90% by weight, diphenyl carbonate: about 9% by weight.

White liquid that was solidified at ambient temperature was continuously removed to the storage tank 48 and contained diphenyl carbonate: about 100% by weight, and butyl phenyl carbonate was below the detection limit. The analysis of the liquid indicated that Ti content was below the detection limit. No deposit or the like were found in the distillation column on inspection.

Example 4 Production of Aromatic Carbonate

Aromatic carbonate was produced using a device shown in FIG. 1. The reaction was carried out by supplying continuously at a rate of about 109 g/Hr, through the preheater 2 and the transport line 1, a mixed solution consisting of dibutyl carbonate, phenol and, as a catalyst, an organic polytitanoxan composition (Matsumoto Trading Co. Ltd. Orgatics TA-22) containing butyl titanate dimer [(BuO)₃—Ti—O—Ti—(OBu)₃] (molecular weight: 550; vapor pressure: 1 Pa or below at 230° C.) (the mixed solution in which the ratio by weight of dibutyl carbonate and phenol was adjusted to 65/35, and Ti as atoms was adjusted to about 10,000 ppm of the whole liquid, and this catalyst was dissolved in this mixture) from the middle stage of the continuous multi-stage distillation column 3, which was composed of a condensation part, which was 2 inch in the internal diameter, 0.5 m in the column length and filled with 10 stages of sieve trays, and a recovery part which was 2 inch in the internal diameter, 1 m in the column length and filled with Dixon packing (6 mmφ).

The condensation part was disposed in the lower part of the stage where the mixture liquid was supplied continuously, and the recovery part was disposed in the upper part. The heat required for the reaction and distillation was supplied by circulating the liquid in the lower part of the column through the line 10 and reboiler 11, and the temperature at the bottom of the multi-stage distillation column was controlled to be about 230° C. The reaction liquid was continuously removed from the bottom of the continuous multi-stage distillation column 3 through the line 10 to a storage tank 12 at 90 g/Hr. After the low boiling point liquid mixture containing 1-butanol as a by-product was removed from the top of the column through a line 4, and then it was liquefied by the cooler 5, and a part of it was removed continuously to the storage tank 8 at 19 g/Hr and the rest was refluxed to the distillation column (reflux ratio=1.9).

The liquid removed to the storage tank 12 was composed of phenol: about 23% by weight, dibutyl carbonate: about 56% by weight, butyl phenyl carbonate: about 12% by weight, diphenyl carbonate: about 0.2% by weight, 1-butanol: about 0.3% by weight and also the catalyst. The liquid removed to the storage tank 8 was composed of 1-butanol: about 99% by weight, phenol: about 0.5% by weight, and dibutyl carbonate: about 0.2% by weight.

After the continuous multi-stage distillation column 3, the reaction was carried out using the continuous multi-stage distillation column 15. The continuous multi-stage distillation column 15, as in the case of the continuous multi-stage distillation column 3, was composed of the condensation part, which is 2 inch in the internal diameter, 0.5 m in the column length and filled with 10 stages of sieve trays, and the recovery part which is 2 inch in the internal diameter, 1 m in the column length and filled with Dixon packing (6 mmφ), and the condensation part was disposed in the lower part of the stage where the reaction liquid containing the catalyst was supplied continuously from the storage tank 12 to this distillation column 15, and the recovery part was disposed in the upper part. The reaction was carried out by supplying continuously through the line 13 the reaction liquid, which was removed from the bottom of the continuous multi-stage distillation column 3 through the line 10 to the storage tank 12, to the continuous multi-stage distillation column 15 at 100 g/Hr after preheating with a preheater 14.

The heat required for the reaction and distillation was supplied by circulating the liquid in the lower part of the column through the line 22 and reboiler 24, and the temperature at the bottom of the multi-stage distillation column was controlled to be about 220° C. The reaction liquid was continuously removed from the bottom of the continuous multi-stage distillation column 15 through the line 22 to a storage tank 24 at 17 g/Hr. After the low boiling point liquid mixture containing dibutylcarbonate as a by-product was removed from the top of the column through a line 16, and then it was liquefied by the cooler 17, and a part of it was removed continuously to a storage tank 20 at 83 g/Hr and the rest was refluxed to the distillation column (reflux ratio=4). The liquid removed to the storage tank 24 was composed of dibutyl carbonate: about 5% by weight, butyl phenyl carbonate: about 74% by weight, diphenyl carbonate: about 10% by weight and also the catalyst. The liquid removed to the storage tank 20 was composed of 1-butanol: about 0.3% by weight, phenol: about 18% by weight, and dibutyl carbonate: about 81% by weight. No deposit or the like were found in the distillation column on inspection.

[Purification of Diaryl Carbonate]

Purification of diaryl carbonate was carried out with the device shown in FIG. 2. The distillation separation was carried out by continuously feeding the liquid, which was removed to the storage tank 24, through the line 25 passing a preheater 26 at about 100 g/Hr to about 0.1 m above the middle stage of the continuous multi-stage distillation column 27, which was a column filled with Dixon packing (6 mmφ) with an internal diameter of 2 inch and a length of 1 m. The heat required for the distillation separation was supplied by circulating the liquid in the lower part of the column through the line 34 and reboiler 35, and the temperature at the bottom of the multi-stage distillation column is controlled to be about 210° C. The bottom liquid was continuously removed from the bottom of the continuous multi-stage distillation column 27 through the line 34 to the storage tank 36 at about 20 g/Hr.

After removing from the top of the column through the line 28, the distillate was liquefied by the cooler 29 and was removed continuously to a storage tank 33 at about 80 g/Hr. The liquid removed to the storage tank 33 is composed of dibutyl carbonate: about 6% by weight, butyl phenyl carbonate: about 86% by weight, diphenyl carbonate: about 7.5% by weight. The distillation separation was carried out by continuously feeding the liquid, which was continuously removed continuously to the storage tank 33, through the line 37 passing a preheater 38 at about 100 g/Hr to the middle stage of the continuous multi-stage distillation column 39, which was a column filled with Dixon packing (6 mmφ) with an internal diameter of 2 inch and 2 m length.

The heat required for the distillation separation was supplied by circulating the liquid in the lower part of the column through the line 46 and reboiler 47, and the temperature at the bottom of the multi-stage distillation column is controlled to be about 230° C. The bottom liquid was continuously removed from the bottom of the continuous multi-stage distillation column 39 through the line 46 to the storage tank 48 at about 8 g/Hr. After removing from the top of the column through the line 40, the distillate was liquefied by the cooler 41 and was removed continuously to the storage tank 44 at about 92 g/Hr. The liquid removed to the storage tank 44 is composed of dibutyl carbonate: about 6% by weight, butyl phenyl carbonate: about 94% by weight. White liquid that was solidified at ambient temperature was continuously removed to the storage tank 48 and contained diphenyl carbonate: about 100% by weight, and butyl phenyl carbonate was below the detection limit. The analysis of the liquid indicated that Ti content was below the detection limit. No deposit or the like were found in the distillation column on inspection.

Example 5 Production of Aromatic Carbonic Acid Ester

Aromatic carbonate was produced using a device shown in FIG. 1. The reaction was carried out by supplying continuously at a rate of about 109 g/Hr, through a preheater 2 and a transport line 1, a mixed solution consisting of dibutyl carbonate, phenol and, as a catalyst, titanium methyl phenoxide (Azumax Co. Ltd. Ti-A KT881) (molecular weight: 476; vapor pressure: 1 Pa or below at 230° C.) (the mixed solution in which the ratio by weight of dibutyl carbonate to phenol was adjusted to 65/35, and Ti as atoms was adjusted to about 10,000 ppm of the whole liquid) from the middle stage of a continuous multi-stage distillation column 3, which was composed of a condensation part, which was 2 inch in the internal diameter, 0.5 m in the column length and filled with 10 stages of sieve trays, and a recovery part which was 2 inch in the internal diameter, 1 m in the column length and filled with Dixon packing (6 mmφ) (at the time of supplying, the catalyst was dissolved in the solution).

The condensation part was disposed in the lower part of the stage where the mixed solution was supplied continuously, and the recovery part was disposed in the upper part. The heat required for the reaction and distillation was supplied by circulating the liquid in the lower part of the column through a line 10 and a reboiler 11, and the temperature at the bottom of the multi-stage distillation column was controlled to be about 230° C. The reaction liquid was continuously removed from the bottom of the continuous multi-stage distillation column 3 through the line 10 to a storage tank 12 at 90 g/Hr. After the low boiling point liquid mixture containing 1-butanol as a by-product was removed from the top of the column through a line 4, and then it was liquefied by the cooler 5, and a part of it was removed continuously to a storage tank 8 at 19 g/Hr and the rest was refluxed to the distillation column (reflux ratio=1.9).

The liquid removed to the storage tank 12 was composed of phenol: about 23% by weight, dibutyl carbonate: about 56% by weight, butyl phenyl carbonate: about 12% by weight, diphenyl carbonate: about 0.2% by weight, 1-butanol: about 0.3% by weight and the catalyst. The liquid removed to the storage tank 8 was composed of 1-butanol: about 99% by weight, phenol: about 0.5% by weight, and dibutyl carbonate: about 0.2% by weight.

After the reaction in the continuous multi-stage distillation column 3, the reaction was carried out using a continuous multi-stage distillation column 15. The continuous multi-stage distillation column 15, as in the case of the continuous multi-stage distillation column 3, was composed of a condensation part, which is 2 inch in the internal diameter, 0.5 m in the column length and filled with 10 stages of sieve trays, and a recovery part which is 2 inch in the internal diameter, 1 m in the column length and filled with Dixon packing (6 mmφ), and the condensation part was disposed in the lower part of the stage where the reaction liquid containing the catalyst was supplied continuously from the storage tank 12 to this distillation column 15, and the recovery part was disposed in the upper part. The reaction was carried out by continuously supplying through a line 13 the reaction liquid, which was removed from the bottom of the continuous multi-stage distillation column 3 through the line 10 to the storage tank 12, to the continuous multi-stage distillation column 15 at 100 g/Hr after preheating with a preheater 14.

The heat required for the reaction and distillation was supplied by circulating the liquid in the lower part of the column through a line 22 and a reboiler 24, and the temperature at the bottom of the multi-stage distillation column was controlled to be about 220° C. The reaction liquid was continuously removed from the bottom of the continuous multi-stage distillation column 15 through the line 22 to a storage tank 24 at 17 g/Hr. After the low boiling point liquid mixture containing dibutylcarbonate as a by-product was removed from the top of the column through a line 16, and then it was liquefied by a cooler 17, and a part of it was removed continuously to a storage tank 20 at 83 g/Hr and the rest was refluxed to the distillation column (reflux ratio=4). The liquid removed to the storage tank 24 was composed of dibutyl carbonate: about 5% by weight, butyl phenyl carbonate: about 74% by weight, diphenyl carbonate: about 10% by weight and the catalyst. The liquid removed to the storage tank 20 was composed of 1-butanol: about 0.3% by weight, phenol: about 18% by weight, and dibutyl carbonate: about 81% by weight. No deposit or the like were found in the distillation column on inspection.

[Purification of Diaryl Carbonate]

Purification of diaryl carbonate was carried out with a device shown in FIG. 2. The distillation separation was carried out by continuously feeding the liquid, which was removed to the storage tank 24, through a line 25 passing a preheater 26 at about 100 g/Hr to about 0.1 m above the middle stage of a continuous multi-stage distillation column 27, which was a column filled with Dixon packing (6 mmφ) with an internal diameter of 2 inch and a length of 1 m. The heat required for the distillation separation was supplied by circulating the liquid in the lower part of the column through a line 34 and a reboiler 35, and the temperature at the bottom of the multi-stage distillation column was controlled to be about 210° C. The bottom liquid was continuously removed from the bottom of the continuous multi-stage distillation column 27 through the line 34 to the storage tank 36 at about 20 g/Hr.

After removing from the top of the column through the line 28, the distillate was liquefied by a cooler 29 and was removed continuously to a storage tank 33 at about 80 g/Hr. The liquid removed to the storage tank 33 is composed of dibutyl carbonate: about 6% by weight, butyl phenyl carbonate: about 86% by weight, diphenyl carbonate: about 7.5% by weight. The distillation separation was carried out by continuously feeding the liquid, which was continuously removed to the storage tank 33, through a line 37 passing a preheater 38 at about 100 g/Hr to the middle stage of a continuous multi-stage distillation column 39, which was a column filled with Dixon packing (6 mmφ) with an internal diameter of 2 inch and a length of 2 m.

The heat required for the distillation separation was supplied by circulating the liquid in the lower part of the column through a line 46 and a reboiler 47, and the temperature at the bottom of the multi-stage distillation column was controlled to be about 230° C. The bottom liquid was continuously removed from the bottom of the continuous multi-stage distillation column 39 through the line 46 to a storage tank 48 at about 8 g/Hr. After removing from the top of the column through a line 40, the distillate was liquefied by a cooler 41 and was removed continuously to the storage tank 44 at about 92 g/Hr. The liquid removed to a storage tank 44 is composed of dibutyl carbonate: about 6% by weight, butyl phenyl carbonate: about 94% by weight. White liquid that was solidified at ambient temperature was continuously removed to a storage tank 48 and contained diphenyl carbonate: about 100% by weight, and butyl phenyl carbonate was below the detection limit. The analysis of the liquid indicated that Ti content was 0.8 ppm. No deposit or the like were found in the distillation column on inspection.

Example 6 Production of Aromatic Carbonate

Aromatic carbonate was produced using a device shown in FIG. 1. The reaction was carried out by supplying continuously at a rate of about 109 g/Hr, through a preheater 2 and a transport line 1, a mixed solution consisting of dibutyl carbonate, phenol and, as a catalyst, an organic polytitanoxan composition (Nippon Soda Co. Ltd. B-4) containing butyl titanate tetramer (molecular weight: 970; vapor pressure: 1 Pa or below at 230° C.), (the mixed solution in which the ratio by weight of dibutyl carbonate to phenol was adjusted to about 65/35, and Ti as atoms was adjusted to about 10,000 ppm of the whole liquid, and this catalyst was dissolved in this solution) from the middle stage of a continuous multi-stage distillation column 3, which was composed of a condensation part, which was 2 inch in the internal diameter, 0.5 m in the column length and filled with 10 stages of sieve trays, and a recovery part which was 2 inch in the internal diameter, 1 m in the column length and filled with Dixon packing (6 mmφ).

The condensation part was disposed in the lower part of the stage where the mixture was supplied continuously, and the recovery part was disposed in the upper part. The heat required for the reaction and distillation was supplied by circulating the liquid in the lower part of the column through a line 10 and a reboiler 11, and the temperature at the bottom of the multi-stage distillation column was controlled to be about 230° C. The reaction liquid was continuously removed from the bottom of the continuous multi-stage distillation column 3 through the line 10 to a storage tank 12 at 90 g/Hr. The catalyst was dissolved in the reaction liquid. After the low boiling point liquid mixture containing 1-butanol as a by-product was removed from the top of the column through a line 4, and then it was liquefied by the cooler 5, and a part of it was removed continuously to a storage tank 8 at 19 g/Hr and the rest was refluxed to the distillation column (reflux ratio=1.9).

The liquid removed to the storage tank 12 was composed of phenol: about 23% by weight, dibutyl carbonate: about 56% by weight, butyl phenyl carbonate: about 12% by weight, diphenyl carbonate: about 0.2% by weight, 1-butanol: about 0.3% by weight and the catalyst. The liquid removed to the storage tank 8 was composed of 1-butanol: about 99% by weight, phenol: about 0.5% by weight, and dibutyl carbonate: about 0.2% by weight.

After the reaction in the continuous multi-stage distillation column 3, the reaction was carried out using a continuous multi-stage distillation column 15. The continuous multi-stage distillation column 15, as in the case of the continuous multi-stage distillation column 3, was composed of a condensation part, which is 2 inch in the internal diameter, 0.5 m in the column length and filled with 10 stages of sieve trays, and a recovery part which is 2 inch in the internal diameter, 1 m in the column length and filled with Dixon packing (6 mmφ), and the condensation part was disposed in the lower part of the stage where the reaction liquid containing the catalyst was supplied continuously from the storage tank 12 to this distillation column 15, and the recovery part was disposed in the upper part. The reaction was carried out by supplying continuously through a line 13 the reaction liquid, which was removed from the bottom of the continuous multi-stage distillation column 3 through the line 10 to the storage tank 12, to the continuous multi-stage distillation column 15 at 100 g/Hr after preheating with a preheater 14.

The heat required for the reaction and distillation was supplied by circulating the liquid in the lower part of the column through a line 22 and a reboiler 24, and the temperature at the bottom of the multi-stage distillation column was controlled to be about 220° C. The reaction liquid was continuously removed from the bottom of the continuous multi-stage distillation column 15 through the line 22 to a storage tank 24 at 17 g/Hr. After the low boiling point liquid mixture containing dibutylcarbonate as a by-product was removed from the top of the column through a line 16, and then it was liquefied by a cooler 17, and a part of it was removed continuously to a storage tank 20 at 83 g/Hr and the rest was refluxed to the distillation column (reflux ratio=4). The liquid removed to the storage tank 24 was composed of dibutyl carbonate: about 5% by weight, butyl phenyl carbonate: about 74% by weight, diphenyl carbonate: about 10% by weight and the catalyst. The liquid removed to the storage tank 20 was composed of 1-butanol: about 0.3% by weight, phenol: about 18% by weight, and dibutyl carbonate: about 81% by weight.

[Purification of Diaryl Carbonate]

Purification of diaryl carbonate was carried out with a device shown in FIG. 2. The distillation separation was carried out by continuously feeding the liquid, which was removed to the storage tank 24, through a line 25 passing a preheater 26 at about 100 g/Hr to about 0.1 m above the middle stage of a continuous multi-stage distillation column 27, which was a column filled with Dixon packing (6 mmφ) with an internal diameter of 2 inch and a length of 1 m. The heat required for the distillation separation was supplied by circulating the liquid in the lower part of the column through a line 34 and a reboiler 35, and the temperature at the bottom of the multi-stage distillation column was controlled to be about 210° C. The bottom liquid was continuously removed from the bottom of the continuous multi-stage distillation column 27 through the line 34 to the storage tank 36 at about 20 g/Hr.

After removing from the top of the column through the line 28, the distillate was liquefied by a cooler 29 and was removed continuously to a storage tank 33 at about 80 g/Hr. The liquid removed to the storage tank 33 is composed of dibutyl carbonate: about 6% by weight, butyl phenyl carbonate: about 86% by weight, diphenyl carbonate: about 7.5% by weight. The distillation separation was carried out by continuously feeding the liquid, which was continuously removed to the storage tank 33, through a line 37 passing a preheater 38 at about 100 g/Hr to the middle stage of a continuous multi-stage distillation column 39, which was a column filled with Dixon packing (6 mmφ) with an internal diameter of 2 inch and a length of 2 m.

The heat required for the distillation separation was supplied by circulating the liquid in the lower part of the column through a line 46 and a reboiler 47, and the temperature at the bottom of the multi-stage distillation column is controlled to be about 230° C. The bottom liquid was continuously removed from the bottom of the continuous multi-stage distillation column 39 through the line 46 to a storage tank 48 at about 8 g/Hr. After removing from the top of the column through the line 40, the distillate was liquefied by the cooler 41 and was removed continuously to the storage tank 44 at about 92 g/Hr. The liquid removed to the storage tank 44 is composed of dibutyl carbonate: about 6% by weight, butyl phenyl carbonate: about 94% by weight. White liquid that was solidified at ambient temperature was continuously removed to a storage tank 48 and contained diphenyl carbonate: about 100% by weight, and butyl phenyl carbonate was below the detection limit. The analysis of the liquid indicated that Ti content was below the detection limit. No deposit or the like were found in the distillation column on inspection.

Example 7 Production of Aromatic Carbonic Acid Ester

Aromatic carbonate was produced using a device shown in FIG. 1. The reaction was carried out by supplying continuously at a rate of about 109 g/Hr, through the preheater 2 and the transport line 1, a mixed solution consisting of dibutyl carbonate, phenol and, as catalyst, monobutyltin butyloxide oxide (molecular weight: 660 or above; vapor pressure: 1 Pa or below at 230° C.) (the mixed solution in which the ratio by weight of dibutyl carbonate to phenol was adjusted to about 65/35, and Tin as atoms was adjusted to about 10,000 ppm of the whole liquid, and this catalyst was dissolved in this solution) from the middle stage of a continuous multi-stage distillation column 3, which was composed of a condensation part, which was 2 inch in the internal diameter, 0.5 m in the column length and filled with 10 stages of sieve trays, and a recovery part which was 2 inch in the internal diameter, 1 m in the column length and filled with Dixon packing (6 mmφ).

The condensation part was disposed in the lower part of the stage where the mixture was supplied continuously, and the recovery part was disposed in the upper part. The heat required for the reaction and distillation was supplied by circulating the liquid in the lower part of the column through a line 10 and a reboiler 11, and the temperature at the bottom of the multi-stage distillation column was controlled to be about 230° C. The reaction liquid was continuously removed from the bottom of the continuous multi-stage distillation column 3 through the line 10 to a storage tank 12 at 90 g/Hr. The catalyst was dissolved in the reaction liquid. After the low boiling point liquid mixture containing 1-butanol as a by-product was removed from the top of the column through a line 4, and then it was liquefied by the cooler 5, and a part of it was removed continuously to a storage tank 8 at 19 g/Hr and the rest was refluxed to the distillation column (reflux ratio=1.9).

The liquid removed to the storage tank 12 was composed of phenol: about 23% by weight, dibutyl carbonate: about 56% by weight, butyl phenyl carbonate: about 12% by weight, diphenyl carbonate: about 0.2% by weight, 1-butanol: about 0.3% by weight and the catalyst. The liquid removed to the storage tank 8 was composed of 1-butanol: about 99% by weight, phenol: about 0.5% by weight, and dibutyl carbonate: about 0.2% by weight.

After the reaction in the continuous multi-stage distillation column 3, the reaction was carried out using a continuous multi-stage distillation column 15. The continuous multi-stage distillation column 15, as in the case of the continuous multi-stage distillation column 3, was composed of a condensation part, which is 2 inch in the internal diameter, 0.5 m in the column length and filled with 10 stages of sieve trays, and a recovery part which is 2 inch in the internal diameter, 1 m in the column length and filled with Dixon packing (6 mmφ), and the condensation part was disposed in the lower part of the stage where the reaction liquid containing the catalyst was supplied continuously from the storage tank 12 to this distillation column 15, and the recovery part was disposed in the upper part. The reaction was carried out by supplying continuously through a line 13 the reaction liquid, which was removed from the bottom of the continuous multi-stage distillation column 3 through the line 10 to the storage tank 12, to the continuous multi-stage distillation column 15 at 100 g/Hr after preheating with a preheater 14.

The heat required for the reaction and distillation was supplied by circulating the liquid in the lower part of the column through a line 22 and a reboiler 24, and the temperature at the bottom of the multi-stage distillation column was controlled to be about 220° C. The reaction liquid was continuously removed from the bottom of the continuous multi-stage distillation column 15 through the line 22 to a storage tank 24 at 17 g/Hr. After the low boiling point liquid mixture containing dibutylcarbonate as a by-product was removed from the top of the column through a line 16, and then it was liquefied by a cooler 17, and a part of it was removed continuously to a storage tank 20 at 83 g/Hr and the rest was refluxed to the distillation column (reflux ratio=4). The liquid removed to the storage tank 24 was composed of dibutyl carbonate: about 5% by weight, butyl phenyl carbonate: about 74% by weight, diphenyl carbonate: about 10% by weight. The liquid removed to the storage tank 20 was composed of 1-butanol: about 0.3% by weight, phenol: about 18% by weight, and dibutyl carbonate: about 81% by weight. No deposit or the like were found in the distillation column on inspection.

[Purification of Diaryl Carbonate]

Purification of diaryl carbonate was carried out with the device shown in FIG. 2. The distillation separation was carried out by continuously feeding the liquid, which was removed to the storage tank 24, through a line 25 passing a preheater 26 at about 100 g/Hr to about 0.1 m above the middle stage of a continuous multi-stage distillation column 27, which was a column filled with Dixon packing (6 mmφ) with an internal diameter of 2 inch and a length of 1 m. The heat required for the distillation separation was supplied by circulating the liquid in the lower part of the column through a line 34 and a reboiler 35, and the temperature at the bottom of the multi-stage distillation column is controlled to be about 210° C. The bottom liquid was continuously removed from the bottom of the continuous multi-stage distillation column 27 through the line 34 to the storage tank 36 at about 20 g/Hr.

After removing from the top of the column through the line 28, the distillate was liquefied by a cooler 29 and was removed continuously to a storage tank 33 at about 80 g/Hr. The liquid removed to the storage tank 33 is composed of dibutyl carbonate: about 6% by weight, butyl phenyl carbonate: about 86% by weight, diphenyl carbonate: about 7.5% by weight. The distillation separation was carried out by continuously feeding the liquid, which was continuously removed to the storage tank 33, through a line 37 passing a preheater 38 at about 100 g/Hr to the middle stage of a continuous multi-stage distillation column 39, which was a column filled with Dixon packing (6 mmφ) with an internal diameter of 2 inch and a length of 2 m.

The heat required for the distillation separation was supplied by circulating the liquid in the lower part of the column through a line 46 and a reboiler 47, and the temperature at the bottom of the multi-stage distillation column was controlled to be about 230° C. The bottom liquid was continuously removed from the bottom of the continuous multi-stage distillation column 39 through the line 46 to a storage tank 48 at about 8 g/Hr. After removing from the top of the column through a line 40, the distillate was liquefied by a cooler 41 and was removed continuously to a storage tank 44 at about 92 g/Hr. The liquid removed to the storage tank 44 is composed of dibutyl carbonate: about 6% by weight, butyl phenyl carbonate: about 94% by weight. White liquid that was solidified at ambient temperature was continuously removed to a storage tank 48 and contained diphenyl carbonate: about 100% by weight, and butyl phenyl carbonate was below the detection limit. The analysis of the liquid indicated that Sn content was 0.9 ppm. No deposit or the like were found in the distillation column on inspection.

Example 8 Production of Aromatic Carbonic Acid Ester

Aromatic carbonate was produced using a device shown in FIG. 1. The reaction was carried out by supplying continuously at a rate of about 109 g/Hr, through a preheater 2 and a line 1, a mixed solution consisting of dibutyl carbonate, phenol and, as a catalyst, titanate containing butyl titanate hexamer [(BuO)₃—Ti—O—(Ti—(OBu)₂.O)₄—Ti—(OBu)₃] (result of element analysis: C=48.3, H=9.1, O=21.9, Ti=20.7; since oxygen derived from BuO is 16.1, the number of bridging oxygen is 5, that is, there are 5 Ti—O—Ti bonds; molecular weight: 1390; vapor pressure: 1 Pa or below at 230° C.) (the mixed solution in which the ratio by weight of dibutyl carbonate to phenol was adjusted to about 65/35, and Ti as atoms was adjusted to about 10,000 ppm of the whole liquid, and this catalyst was dissolved in this solution) from the middle stage of the continuous multi-stage distillation column 3, which was composed of a condensation part, which was 2 inch in the internal diameter, 0.5 m in the column length and filled with 10 stages of sieve trays, and a recovery part which was 2 inch in the internal diameter, 1 m in the column length and filled with Dixon packing (6 mmφ).

The condensation part was disposed in the lower part of the stage where the mixture was supplied continuously, and the recovery part was disposed in the upper part. The heat required for the reaction and distillation was supplied by circulating the liquid in the lower part of the column through a line 10 and a reboiler 11, and the temperature at the bottom of the multi-stage distillation column was controlled to be about 230° C. The reaction liquid was continuously removed from the bottom of the continuous multi-stage distillation column 3 through the line 10 to a storage tank 12 at 90 g/Hr. The catalyst was dissolved in the reaction liquid. After the low boiling point liquid mixture containing 1-butanol as a by-product was removed from the top of the column through a line 4, and then it was liquefied by the cooler 5, and a part of it was removed continuously to a storage tank 8 at 19 g/Hr and the rest was refluxed to the distillation column (reflux ratio=1.9).

The liquid removed to the storage tank 12 was composed of phenol: about 23% by weight, dibutyl carbonate: about 56% by weight, butyl phenyl carbonate: about 12% by weight, diphenyl carbonate: about 0.2% by weight, 1-butanol: about 0.3% by weight and also the catalyst. The liquid removed to the storage tank 8 was composed of 1-butanol: about 99% by weight, phenol: about 0.5% by weight, and dibutyl carbonate: about 0.2% by weight.

After the reaction in the continuous multi-stage distillation column 3, the reaction was carried out using a continuous multi-stage distillation column 15. The continuous multi-stage distillation column 15, as in the case of the continuous multi-stage distillation column 3, was composed of a condensation part, which is 2 inch in the internal diameter, 0.5 m in the column length and filled with 10 stages of sieve trays, and a recovery part which is 2 inch in the internal diameter, 1 m in the column length and filled with Dixon packing (6 mmφ), and the condensation part was disposed in the lower part of the stage where the reaction liquid containing the catalyst was supplied continuously from the storage tank 12 to this distillation column 15, and the recovery part was disposed in the upper part. The reaction was carried out by supplying continuously through a line 13 the reaction liquid, which was removed from the bottom of the continuous multi-stage distillation column 3 through the line 10 to the storage tank 12, to the continuous multi-stage distillation column 15 at 100 g/Hr after preheating with a preheater 14.

The heat required for the reaction and distillation was supplied by circulating the liquid in the lower part of the column through a line 22 and a reboiler 24, and the temperature at the bottom of the multi-stage distillation column was controlled to be about 220° C. The reaction liquid was continuously removed from the bottom of the continuous multi-stage distillation column 15 through the line 22 to a storage tank 24 at 17 g/Hr. After the low boiling point liquid mixture containing dibutylcarbonate as a by-product was removed from the top of the column through a line 16, and then it was liquefied by a cooler 17, and a part of it was removed continuously to a storage tank 20 at 83 g/Hr and the rest was refluxed to the distillation column (reflux ratio=4). The liquid removed to the storage tank 24 was composed of dibutyl carbonate: about 5% by weight, butyl phenyl carbonate: about 74% by weight, diphenyl carbonate: about 10% by weight and the catalyst. The liquid removed to the storage tank 20 was composed of 1-butanol: about 0.3% by weight, phenol: about 18% by weight, and dibutyl carbonate: about 81% by weight. No deposit or the like were found in the distillation column on inspection.

[Purification of Diaryl Carbonate]

Purification of diaryl carbonate was carried out with a device shown in FIG. 2. The distillation separation was carried out by continuously feeding the liquid, which was removed to the storage tank 24, through a line 25 passing a preheater 26 at about 100 g/Hr to about 0.1 m above the middle stage of a continuous multi-stage distillation column 27, which was a column filled with Dixon packing (6 mmφ) with an internal diameter of 2 inch and a length of 1 m. The heat required for the distillation separation was supplied by circulating the liquid in the lower part of the column through the line 34 and reboiler 35, and the temperature at the bottom of the multi-stage distillation column is controlled to be about 210° C. The bottom liquid was continuously removed from the bottom of the continuous multi-stage distillation column 27 through the line 34 to the storage tank 36 at about 20 g/Hr.

After removing from the top of the column through the line 28, the distillate was liquefied by a cooler 29 and was removed continuously to a storage tank 33 at about 80 g/Hr. The liquid removed to the storage tank 33 is composed of dibutyl carbonate: about 6% by weight, butyl phenyl carbonate: about 86% by weight, diphenyl carbonate: about 7.5% by weight. The distillation separation was carried out by continuously feeding the liquid, which was continuously removed to the storage tank 33, through a line 37 passing a preheater 38 at about 100 g/Hr to the middle stage of a continuous multi-stage distillation column 39, which was a column filled with Dixon packing (6 mmφ) with an internal diameter of 2 inch and a length of 2 m.

The heat required for the distillation separation was supplied by circulating the liquid in the lower part of the column through a line 46 and a reboiler 47, and the temperature at the bottom of the multi-stage distillation column is controlled to be about 230° C. The bottom liquid was continuously removed from the bottom of the continuous multi-stage distillation column 39 through the line 46 to the storage tank 48 at about 8 g/Hr. After removing from the top of the column through the line 40, the distillate was liquefied by the cooler 41 and was removed continuously to the storage tank 44 at about 92 g/Hr. The liquid removed to a storage tank 44 is composed of dibutyl carbonate: about 6% by weight, butyl phenyl carbonate: about 94% by weight. White liquid that was solidified at ambient temperature was continuously removed to the storage tank 48 and contained diphenyl carbonate: about 100% by weight, and butyl phenyl carbonate was below the detection limit. The analysis of the liquid indicated that Ti content was below the detection limit. No deposit or the like were found in the distillation column on inspection.

Example 9 Production of Aromatic Carbonic Acid Ester

Aromatic carbonate was produced using a device shown in FIG. 1. The reaction was carried out by supplying continuously at a rate of about 109 g/Hr, through a preheater 2 and a line 1, a mixed solution consisting of dibutyl carbonate, phenol and, as a catalyst, an adduct with phenol of phenyl titanate tetramer [(PhO)₃—Ti—O—(Ti(OPh)₂—O)₂—Ti—(OPh)₃] (result of element analysis: C=65.2, H=4.8, O=17.6, Ti=12.4; According to ¹H-NMR analysis, PhOH and PhO groups exist at a ratio of 4:10. In one molecule, there are 4 Ti atoms and 3 oxygen atoms not derived from PhOH and PhO groups, that is, the number of bridging oxygen atoms is 3, and therefore 3 Ti—O—Ti bonds exist; molecular weight without the adduct phenol: 1170; vapor pressure: 1 Pa or below at 230° C.) (the mixed solution in which the ratio by weight of dibutyl carbonate to phenol was adjusted to about 65/35, and Ti as atoms was adjusted to about 10,000 ppm of the whole liquid) consisting of dibutyl carbonate, phenol and, as a catalyst, an adduct with phenol of phenyl titanate tetramer [(PhO)₃—Ti—O—(Ti(OPh)₂—O)₂—Ti—(OPh)₃] (result of element analysis: C=65.2, H=4.8, O=17.6, Ti=12.4; According to ¹H-NMR analysis, PhOH and PhO groups exist at a ratio of 4:10. In one molecule, there are 4 Ti atoms and 3 oxygen atoms not derived from PhOH and PhO groups, that is, the number of bridging oxygen atoms is 3, and therefore 3 Ti—O—Ti bonds exist; molecular weight without the adduct phenol: 1170; vapor pressure: 1 Pa or below at 230° C.) from the middle stage of the continuous multi-stage distillation column 3, which was composed of a condensation part, which was 2 inch in the internal diameter, 0.5 m in the column length and filled with 10 stages of sieve trays, and a recovery part which was 2 inch in the internal diameter, 1 m in the column length and filled with Dixon packing (6 mmφ).

The condensation part was disposed in the lower part of the stage where the mixture was supplied continuously, and the recovery part was disposed in the upper part. The heat required for the reaction and distillation was supplied by circulating the liquid in the lower part of the column through a line 10 and a reboiler 11, and the temperature at the bottom of the multi-stage distillation column was controlled to be about 230° C. The reaction liquid was continuously removed from the bottom of the continuous multi-stage distillation column 3 through the line 10 to a storage tank 12 at 90 g/Hr. After the low boiling point liquid mixture containing 1-butanol as a by-product was removed from the top of the column through a line 4, and then it was liquefied by the cooler 5, and a part of it was removed continuously to a storage tank 8 at 19 g/Hr and the rest was refluxed to the distillation column (reflux ratio=1.9). The catalyst was dissolved in the liquid phase.

The liquid removed to the storage tank 12 was composed of phenol: about 23% by weight, dibutyl carbonate: about 56% by weight, butyl phenyl carbonate: about 12% by weight, diphenyl carbonate: about 0.2% by weight, 1-butanol: about 0.3% by weight and the catalyst. The liquid removed to the storage tank 8 was composed of 1-butanol: about 99% by weight, phenol: about 0.5% by weight, and dibutyl carbonate: about 0.2% by weight.

After the reaction in the continuous multi-stage distillation column 3, the reaction was carried out using a continuous multi-stage distillation column 15. The continuous multi-stage distillation column 15, as in the case of the continuous multi-stage distillation column 3, was composed of a condensation part, which is 2 inch in the internal diameter, 0.5 m in the column length and filled with 10 stages of sieve trays, and a recovery part which is 2 inch in the internal diameter, 1 m in the column length and filled with Dixon packing (6 mmφ), and the condensation part was disposed in the lower part of the stage where the reaction liquid containing the catalyst was supplied continuously from the storage tank 12 to this distillation column 15, and the recovery part was disposed in the upper part. The reaction was carried out by supplying continuously through a line 13 the reaction liquid, which was removed from the bottom of the continuous multi-stage distillation column 3 through the line 10 to the storage tank 12, to the continuous multi-stage distillation column 15 at 100 g/Hr after preheating with a preheater 14.

The heat required for the reaction and distillation was supplied by circulating the liquid in the lower part of the column through a line 22 and a reboiler 24, and the temperature at the bottom of the multi-stage distillation column was controlled to be about 220° C. The reaction liquid was continuously removed from the bottom of the continuous multi-stage distillation column 15 through the line 22 to a storage tank 24 at 17 g/Hr. After the low boiling point liquid mixture containing dibutylcarbonate as a by-product was removed from the top of the column through a line 16, and then it was liquefied by a cooler 17, and a part of it was removed continuously to a storage tank 20 at 83 g/Hr and the rest was refluxed to the distillation column (reflux ratio=4). The liquid removed to the storage tank 24 was composed of dibutyl carbonate: about 5% by weight, butyl phenyl carbonate: about 74% by weight, diphenyl carbonate: about 10% by weight and the catalyst. The liquid removed to the storage tank 20 was composed of 1-butanol: about 0.3% by weight, phenol: about 18% by weight, and dibutyl carbonate: about 81% by weight. No deposit or the like were found in the distillation column on inspection.

[Purification of Diaryl Carbonate]

Purification of diaryl carbonate was carried out with a device shown in FIG. 2. The distillation separation was carried out by continuously feeding the liquid, which was removed to the storage tank 24, through a line 25 passing a preheater 26 at about 100 g/Hr to about 0.1 m above the middle stage of a continuous multi-stage distillation column 27, which was a column filled with Dixon packing (6 mmφ) with an internal diameter of 2 inch and a length of 1 m. The heat required for the distillation separation was supplied by circulating the liquid in the lower part of the column through a line 34 and a reboiler 35, and the temperature at the bottom of the multi-stage distillation column was controlled to be about 210° C. The bottom liquid was continuously removed from the bottom of the continuous multi-stage distillation column 27 through the line 34 to the storage tank 36 at about 20 g/Hr.

After removing from the top of the column through the line 28, the distillate was liquefied by a cooler 29 and was removed continuously to a storage tank 33 at about 80 g/Hr. The liquid removed to the storage tank 33 is composed of dibutyl carbonate: about 6% by weight, butyl phenyl carbonate: about 86% by weight, diphenyl carbonate: about 7.5% by weight. The distillation separation was carried out by continuously feeding the liquid, which was continuously removed to the storage tank 33, through a line 37 passing a preheater 38 at about 100 g/Hr to the middle stage of a continuous multi-stage distillation column 39, which was a column filled with Dixon packing (6 mmφ) with an internal diameter of 2 inch and a length of 2 m.

The heat required for the distillation separation was supplied by circulating the liquid in the lower part of the column through a line 46 and a reboiler 47, and the temperature at the bottom of the multi-stage distillation column was controlled to be about 230° C. The bottom liquid was continuously removed from the bottom of the continuous multi-stage distillation column 39 through the line 46 to the storage tank 48 at about 8 g/Hr. After removing from the top of the column through the line 40, the distillate was liquefied by a cooler 41 and was removed continuously to a storage tank 44 at about 92 g/Hr. The liquid removed to a storage tank 44 is composed of dibutyl carbonate: about 6% by weight, butyl phenyl carbonate: about 94% by weight. White liquid that was solidified at ambient temperature was continuously removed to a storage tank 48 and contained diphenyl carbonate: about 100% by weight, and butyl phenyl carbonate was below the detection limit. The analysis of the liquid indicated that Ti content was below the detection limit. No deposit or the like were found in the distillation column on inspection.

Example 10 Preparation of the Catalyst

To a reaction flask equipped with a stirrer, a thermometer, a heating and cooling device and a reflux condenser, 3400 g (10 mol) of tetra-n-butoxytitanium and 1700 g of n-butanol were added and the liquid was cooled to a temperature of 0° C. while being mixed well. While maintaining the liquid temperature at 0° C., a mixture of 90 g (5 mol) of water and 2000 g of n-butanol was added slowly for 1 hour. After the addition the temperature was raised to 80° C. and stirred for 5 hours. The flask was connected to a rotary evaporator equipped with a vacuum controller, vacuum pump and oil bath for heating after cooling down the liquid to room temperature (about 20° C.). The low boiling point components were distilled by reducing the pressure to about 25K Pa while maintaining the liquid temperature at 80° C. When almost all the distillates came out, the temperature was raised slowly to 230° C. and further the pressure was reduced to 1 Pa, and after confirming that there were no distillate, nitrogen was added to return to normal pressure and the temperature was returned to room temperature (about 20° C.) to obtain about 2750 g of a pale yellow viscous liquid. This liquid is a catalyst A. The result of element analysis showed that the composition is C, 52.3%, H, 9.9%, Q: 20.4%, Ti: 17.4% and there is one Ti—O—Ti bond since the number of oxygen atoms except for the oxygen derived from BuO was 1 against Ti atom 2. Thus the catalyst A described above is presumed to be a mixture containing butyl titanate dimer [(BuO)₃—Ti—O—Ti (OBu)₃] as a main component.

[Production of Aromatic Carbonic Acid Ester]

Aromatic carbonate was produced using a device shown in FIG. 1. The reaction was carried out by supplying continuously at a rate of about 109 g/Hr, through a preheater 2 and a line 1, a mixed solution consisting of dibutyl carbonate, phenol and, as a catalyst, the catalyst A (the mixed solution in which the ratio by weight of dibutyl carbonate to phenol was adjusted to about 65/35, and Ti as atoms was adjusted to about 10,000 ppm of the whole liquid, and this catalyst was dissolved in this solution) from the middle stage of a continuous multi-stage distillation column 3, which was composed of a condensation part, which was 2 inch in the internal diameter, 0.5 m in the column length and filled with 10 stages of sieve trays, and a recovery part which was 2 inch in the internal diameter, 1 m in the column length and filled with Dixon packing (6 mmφ).

The condensation part was disposed in the lower part of the stage where the mixture was supplied continuously, and the recovery part was disposed in the upper part. The heat required for the reaction and distillation was supplied by circulating the liquid in the lower part of the column through a line 10 and a reboiler 11, and the temperature at the bottom of the multi-stage distillation column was controlled to be about 230° C. The reaction liquid was continuously removed from the bottom of the continuous multi-stage distillation column 3 through the line 10 to a storage tank 12 at 90 g/Hr. The catalyst was dissolved in the reaction liquid. After the low boiling point liquid mixture containing 1-butanol as a by-product was removed from the top of the column through a line 4, and then it was liquefied by the cooler 5, and a part of it was removed continuously to a storage tank 8 at 19 g/Hr and the rest was refluxed to the distillation column (reflux ratio=1.9).

The liquid removed to the storage tank 12 was composed of phenol: about 23% by weight, dibutyl carbonate: about 56% by weight, butyl phenyl carbonate: about 12% by weight, diphenyl carbonate: about 0.2% by weight, 1-butanol: about 0.3% by weight and also the catalyst. The liquid removed to the storage tank 8 was composed of 1-butanol: about 99% by weight, phenol: about 0.5% by weight, and dibutyl carbonate: about 0.2% by weight.

After the reaction in the continuous multi-stage distillation column 3, the reaction was carried out using a continuous multi-stage distillation column 15. The continuous multi-stage distillation column 15, as in the case of the continuous multi-stage distillation column 3, was composed of a condensation part, which is 2 inch in the internal diameter, 0.5 m in the column length and filled with 10 stages of sieve trays, and a recovery part which is 2 inch in the internal diameter, 1 m in the column length and filled with Dixon packing (6 mmφ), and the condensation part was disposed in the lower part of the stage where the reaction liquid containing the catalyst was supplied continuously from the storage tank 12 to this distillation column 15, and the recovery part was disposed in the upper part. The reaction was carried out by supplying continuously through a line 13 the reaction liquid, which was removed from the bottom of the continuous multi-stage distillation column 3 through the line 10 to the storage tank 12, to the continuous multi-stage distillation column 15 at 100 g/Hr after preheating with a preheater 14.

The heat required for the reaction and distillation was supplied by circulating the liquid in the lower part of the column through a line 22 and a reboiler 24, and the temperature at the bottom of the multi-stage distillation column was controlled to be about 220° C. The reaction liquid was continuously removed from the bottom of the continuous multi-stage distillation column 15 through the line 22 to a storage tank 24 at 17 g/Hr. After the low boiling point liquid mixture containing dibutylcarbonate as a by-product was removed from the top of the column through a line 16, and then it was liquefied by a cooler 17, and a part of it was removed continuously to a storage tank 20 at 83 g/Hr and the rest was refluxed to the distillation column (reflux ratio=4). The liquid removed to the storage tank 24 was composed of dibutyl carbonate: about 5% by weight, butyl phenyl carbonate: about 74% by weight, diphenyl carbonate: about 10% by weight and the catalyst. The liquid removed to the storage tank 20 was composed of 1-butanol: about 0.3% by weight, phenol: about 18% by weight, and dibutyl carbonate: about 81% by weight. No deposit or the like were found in the distillation column on inspection.

[Purification of Diaryl Carbonate]

Purification of diaryl carbonate was carried out with a device shown in FIG. 2. The distillation separation was carried out by continuously feeding the liquid, which was removed to the storage tank 24, through a line 25 passing a preheater 26 at about 100 g/Hr to about 0.1 m above the middle stage of a continuous multi-stage distillation column 27, which was a column filled with Dixon packing (6 mmφ) with an internal diameter of 2 inch and a length of 1 m. The heat required for the distillation separation was supplied by circulating the liquid in the lower part of the column through a line 34 and a reboiler 35, and the temperature at the bottom of the multi-stage distillation column is controlled to be about 210° C. The bottom liquid was continuously removed from the bottom of the continuous multi-stage distillation column 27 through the line 34 to the storage tank 36 at about 20 g/Hr.

After removing from the top of the column through the line 28, the distillate was liquefied by cooler 29 and was removed continuously to a storage tank 33 at about 80 g/Hr. The liquid removed to the storage tank 33 is composed of dibutyl carbonate: about 6% by weight, butyl phenyl carbonate: about 86% by weight, diphenyl carbonate: about 7.5% by weight. The distillation separation was carried out by continuously feeding the liquid, which was continuously removed to the storage tank 33, through a line 37 passing a preheater 38 at about 100 g/Hr to the middle stage of a continuous multi-stage distillation column 39, which was a column filled with Dixon packing (6 mmφ) with an internal diameter of 2 inch and a length of 2 m.

The heat required for the distillation separation was supplied by circulating the liquid in the lower part of the column through a line 46 and a reboiler 47, and the temperature at the bottom of the multi-stage distillation column was controlled to be about 230° C. The bottom liquid was continuously removed from the bottom of the continuous multi-stage distillation column 39 through the line 46 to a storage tank 48 at about 8 g/Hr. After removing from the top of the column through a line 40, the distillate was liquefied by a cooler 41 and was removed continuously to a storage tank 44 at about 92 g/Hr. The liquid removed to the storage tank 44 is composed of dibutyl carbonate: about 6% by weight, butyl phenyl carbonate: about 94% by weight. White liquid that was solidified at ambient temperature was continuously removed to a storage tank 48 and contained diphenyl carbonate: about 100% by weight, and butyl phenyl carbonate was below the detection limit. The analysis of the liquid indicated that Ti content was below the detection limit. No deposit or the like were found in the distillation column on inspection.

Example 11 Preparation of the Catalyst

To a reaction flask equipped with a stirrer, a thermometer, a heating and cooling device and a reflux condenser, 3400 g (10 mol) of tetra-n-butoxytitanium and 1700 g of n-butanol were added and the liquid was cooled to a temperature of 0° C. while being mixed well. While maintaining the liquid temperature at 0° C., a mixture of 216 g (12 mol) of water and 2000 g of n-butanol was added slowly for 1 hour. After the addition the temperature was raised to 80° C. and stirred for 5 hours. The flask was connected to a rotary evaporator equipped with a vacuum controller, vacuum pump and oil bath for heating after cooling down the liquid to room temperature (about 20° C.). The low boiling point components were distilled by reducing the pressure to about 25K Pa while maintaining the liquid temperature at 80° C. When almost all the distillates came out, the temperature was raised slowly to 230° C. and further the pressure was reduced to 1 Pa, and after confirming that there were no distillate, nitrogen was added to return to normal pressure and the temperature was returned to room temperature (about 20° C.) to obtain about 2320 g of pale yellow viscous liquid. This liquid is a catalyst B. The result of element analysis showed that the composition is C, 48.3%, H, 9.1%, O: 21.9%, Ti: 20.7%, and the number of bridging oxygen atoms was 5 since the oxygen atom derived from BuO was 16.1, and there were 5 Ti—O—Ti bonds. The molecular weight was 1390 and the vapor pressure was 1 Pa or less at 230° C. Thus the catalyst B described above is presumed to be a mixture containing butyl titanate hexamer [(BuO)₃—Ti—O—(Ti(OBu)₂—O)₄—Ti—(OBu)₃] as a main component.

[Production of Aromatic Carbonic Acid Ester]

Aromatic carbonate was produced using a device shown in FIG. 1. The reaction was carried out by supplying continuously at a rate of about 109 g/Hr, through a preheater 2 and a line 1, a mixed solution consisting of dibutyl carbonate, phenol and, as a catalyst, the catalyst B (in which the ratio by weight of dibutyl carbonate to phenol was adjusted to about 65/35, and Ti as atoms was adjusted to about 10,000 ppm of the whole liquid, and this catalyst was dissolved in this solution) from the middle stage of a continuous multi-stage distillation column 3, which was composed of a condensation part, which was 2 inch in the internal diameter, 0.5 m in the column length and filled with 10 stages of sieve trays, and a recovery part which was 2 inch in the internal diameter, 1 m in the column length and filled with Dixon packing (6 mmφ).

The condensation part was disposed in the lower part of the stage where the mixture was supplied continuously, and the recovery part was disposed in the upper part. The heat required for the reaction and distillation was supplied by circulating the liquid in the lower part of the column through a line 10 and a reboiler 11, and the temperature at the bottom of the multi-stage distillation column was controlled to be about 230° C. The reaction liquid was continuously removed from the bottom of the continuous multi-stage distillation column 3 through the line 10 to a storage tank 12 at 90 g/Hr. The catalyst was dissolved in the reaction liquid. After the low boiling point liquid mixture containing 1-butanol as a by-product was removed from the top of the column through a line 4, and then it was liquefied by the cooler 5, and a part of it was removed continuously to a storage tank 8 at 19 g/Hr and the rest was refluxed to the distillation column (reflux ratio=1.9).

The liquid removed to the storage tank 12 was composed of phenol: about 23% by weight, dibutyl carbonate: about 56% by weight, butyl phenyl carbonate: about 12% by weight, diphenyl carbonate: about 0.2% by weight, 1-butanol: about 0.3% by weight and also the catalyst. The liquid removed to the storage tank 8 was composed of 1-butanol: about 99% by weight, phenol: about 0.5% by weight, and dibutyl carbonate: about 0.2% by weight.

After the reaction in the continuous multi-stage distillation column 3, the reaction was carried out using a continuous multi-stage distillation column 15. The continuous multi-stage distillation column 15, like the continuous multi-stage distillation column 3, was composed of a condensation part, which is 2 inch in the internal diameter, 0.5 m in the column length and filled with 10 stages of sieve trays, and a recovery part which is 2 inch in the internal diameter, 1 m in the column length and filled with Dixon packing (6 mmφ), and the condensation part was disposed in the lower part of the stage where the reaction liquid containing the catalyst was supplied continuously from the storage tank 12 to this distillation column 15, and the recovery part was disposed in the upper part. The reaction was carried out by supplying continuously through a line 13 the reaction liquid, which was removed from the bottom of the continuous multi-stage distillation column 3 through the line 10 to the storage tank 12, to the continuous multi-stage distillation column 15 at 100 g/Hr after preheating with a preheater 14.

The heat required for the reaction and distillation was supplied by circulating the liquid in the lower part of the column through a line 22 and a reboiler 24, and the temperature at the bottom of the multi-stage distillation column was controlled to be about 220° C. The reaction liquid was continuously removed from the bottom of the continuous multi-stage distillation column 15 through the line 22 to a storage tank 24 at 17 g/Hr. After the low boiling point liquid mixture containing dibutylcarbonate as a by-product was removed from the top of the column through a line 16, and then it was liquefied by a cooler 17, and a part of it was removed continuously to a storage tank 20 at 83 g/Hr and the rest was refluxed to the distillation column (reflux ratio=4). The liquid removed to the storage tank 24 was composed of dibutyl carbonate: about 5% by weight, butyl phenyl carbonate: about 74% by weight, diphenyl carbonate: about 10% by weight and the catalyst. The liquid removed to the storage tank 20 was composed of 1-butanol: about 0.3% by weight, phenol: about 18% by weight, and dibutyl carbonate: about 81% by weight. No deposit or the like were found in the distillation column on inspection.

[Purification of Diaryl Carbonate]

Purification of diaryl carbonate was carried out with the device shown in FIG. 2. The distillation separation was carried out by continuously feeding the liquid, which was removed to the storage tank 24, through a line 25 passing a preheater 26 at about 100 g/Hr to about 0.1 m above the middle stage of a continuous multi-stage distillation column 27, which was a column filled with Dixon packing (6 mmφ) with an internal diameter of 2 inch and a length of 1 m. The heat required for the distillation separation was supplied by circulating the liquid in the lower part of the column through a line 34 and a reboiler 35, and the temperature at the bottom of the multi-stage distillation column is controlled to be about 210° C. The bottom liquid was continuously removed from the bottom of the continuous multi-stage distillation column 27 through the line 34 to the storage tank 36 at about 20 g/Hr.

After removing from the top of the column through the line 28, the distillate was liquefied by a cooler 29 and was removed continuously to a storage tank 33 at about 80 g/Hr. The liquid removed to the storage tank 33 is composed of dibutyl carbonate: about 6% by weight, butyl phenyl carbonate: about 86% by weight, diphenyl carbonate: about 7.5% by weight. The distillation separation was carried out by continuously feeding the liquid, which was continuously removed to the storage tank 33, through a line 37 passing a preheater 38 at about 100 g/Hr to the middle stage of a continuous multi-stage distillation column 39, which was a column filled with Dixon packing (6 mmφ) with an internal diameter of 2 inch and a length of 2 m.

The heat required for the distillation separation was supplied by circulating the liquid in the lower part of the column through a line 46 and a reboiler 47, and the temperature at the bottom of the multi-stage distillation column was controlled to be about 230° C. The bottom liquid was continuously removed from the bottom of the continuous multi-stage distillation column 39 through the line 46 to a storage tank 48 at about 8 g/Hr. After removing from the top of the column through a line 40, the distillate was liquefied by a cooler 41 and was removed continuously to the storage tank 44 at about 92 g/Hr. The liquid removed to the storage tank 44 is composed of dibutyl carbonate: about 6% by weight, butyl phenyl carbonate: about 94% by weight. White liquid that was solidified at ambient temperature was continuously removed to a storage tank 48 and contained diphenyl carbonate: about 100% by weight, and butyl phenyl carbonate was below the detection limit. The analysis of the liquid indicated that Ti content was below the detection limit. No deposit or the like were found in the distillation column on inspection.

Example 12 Preparation of the Catalyst

To a reaction flask equipped with a stirrer, a thermometer, a heating and cooling device and a reflux condenser, 3400 g (10 mol) of tetra-n-butoxytitanium and 1700 g of n-butanol were added and the liquid was cooled to a temperature of 0° C. while being mixed well. While maintaining the liquid temperature at 0° C., a mixture of 90 g (5 mol) of water and 2000 g of n-butanol was added slowly for 1 hour. After the addition the temperature was raised to 80° C. and stirred for 5 hours. The flask was connected to a rotary evaporator equipped with a vacuum controller, vacuum pump and oil bath for heating after cooling down the liquid to room temperature (about 20° C.). The low boiling point components were distilled by reducing the pressure to about 25K Pa while maintaining the liquid temperature at 80° C. When almost all the distillates came out, the temperature was raised slowly to 230° C. and further the pressure was reduced to 1 Pa, and after confirming that there were no distillate, nitrogen was added to return to normal pressure and the temperature was returned to room temperature (about 20° C.) to obtain about 2750 g of pale yellow viscous liquid. This liquid is a catalyst A. The result of element analysis showed that the composition is C, 52.3%, H, 9.9%, O: 20.4%, Ti: 17.4%, and there is one Ti—O—Ti bond since the number of oxygen atoms except for the oxygen derived from BuO was 1 against Ti atom 2. Thus the catalyst A described above is presumed to be a mixture containing butyl titanate dimer [(BuO)₃—Ti—O—Ti(OBu)₃] as a main component.

To this flask, the stirrer, thermometer, heating and cooling device and reflux condenser were reattached and the liquid was heated to 80° C. while stirring. While keeping the liquid temperature at 80° C., 4700 g (50 mol) of distilled and dehydrated phenol was added slowly. After the addition, the liquid was heated to 180° C. and low boiling point components were evaporated. When there was almost no distillate, the temperature of the liquid was slowly raised to 230° C. to remove distillates further. The flask was connected to the vacuum controller and vacuum pump, the pressure was reduced slowly to 1 Pa and distillates were removed. Then the flask was taken out of the oil bath, cooled to room temperature (about 20° C.) and the inside pressure of the flask was returned to normal by nitrogen. Solid substance of about 4300 g with red orange coloring was obtained. This was the catalyst C. The result of element analysis showed that the composition is C, 64.5%, H, 4.5%, O: 16.7%, Ti: 14.3%. The catalyst C described above is presumed to be a mixture containing phenol adduct of phenyl titanate dimer [(PhO)₃—Ti—O—Ti(OPh)₃.2PhOH] as a main component.

[Production of Aromatic Carbonic Acid Ester]

A mixture consisting of dimethyl carbonate, phenol and, as a catalyst, the catalyst C was continuously supplied as a liquid from an inlet line 50 through a preheater 51 to the location at 1 m from the top of a multi-stage distillation column 49 as shown in FIG. 3, which was composed of a packed column with 4 m tall and 3 inch internal diameter filled with Dixon packing (6 mmφ) made of stainless steel. The heat required for the reaction and distillation was supplied by heating the liquid in the bottom of the column by the reboiler (the liquid supply from the inlet line 50: 3.4 kg/Hr; composition of the liquid supply: DMC=about 68.3% by weight, PhOH=about 33.7% by weight, catalyst C=13.5 mmol/Kg). The temperature at the bottom of the column was about 201° C., the pressure at the top of the column was about 800 KPa, the reflux ratio was about 1. As the result of the reaction, the liquid containing the component of the catalyst, and methyl phenyl carbonate and diphenyl carbonate, which were the reaction products, was obtained from the bottom 53 of the column through lines 58 and 60. The gas distillate from a line 54 disposed on the top 52 of the column was condensed by a condenser 55. A part of the condensed liquid was refluxed to a distillation column 49 through an inlet line 56, and the rest was removed from a line 57. From this condensed liquid a low boiling point product, methanol, was obtained. The amount of liquid removed from the line 60 (average liquid composition: methyl phenyl carbonate=50 g/Kg·Hr, diphenyl carbonate=0.4 g/Kg/Hr) was about 2.3 Kg/Hr. No deposit or the like were found in the distillation column on inspection.

[Purification of Aromatic Carbonate]

Aromatic carbonate was purified using a device shown in FIG. 2. The device was a continuous multi-stage distillation column which was composed of a column with 2 inch internal diameter and 1 m height, filled with Dixon packing (6 mmφ). Distillation separation was carried out by feeding the liquid removed from the aforementioned line 60, continuously at a rate of about 100 g/Hr, through a line 25 and a preheater 26, to a continuous multi-stage distillation column 27 at the location about 0.1 m above the middle stage. The heat required for the distillation separation was supplied by circulating the liquid in the lower part of the column through a line 34 and a reboiler 35, and the temperature at the bottom of the multi-stage distillation column was controlled to be about 210° C. The bottom liquid was continuously removed from the bottom of the continuous multi-stage distillation column 27 through the line 34 to the storage tank 36. After removing from the top of the column through a line 28, the distillate was liquefied by a cooler 29 and was removed continuously to a storage tank 33. Distillation separation was carried out by feeding the liquid, which was removed continuously from the storage tank 33, continuously at a rate of about 100 g/Hr, through a line 37 and the preheater 38, to the middle stage of a continuous multi-stage distillation column 39, which was composed of a column with 2 inch internal diameter and 2 m height, filled with Dixon packing (6 mmφ). The heat required for the distillation separation was supplied by circulating the liquid in the lower part of the column through a line 46 and a reboiler 47, and the temperature at the bottom of the multi-stage distillation column was controlled to be about 230° C. The bottom liquid was continuously removed from the bottom of the continuous multi-stage distillation column 39 through a line 46 to a storage tank 48. After being removed from the top of the column through a line 40, the distillate was liquefied by a cooler 41 and was removed continuously to a storage tank 44. The liquid removed to the storage tank 44 contained methyl phenyl carbonate at about 94% by weight. The analysis of the liquid indicated that Ti content was below the detection limit. No deposit or the like were found in the distillation column on inspection.

Comparative Example 2

Aromatic carbonate was purified as in Example 12 except that the catalyst was changed from the catalyst C to phenoxy titanate [Ti(OPh)₄] (molecular weight: 420, vapor pressure: about 15 Pa at 230° C.). The amount of the liquid (average composition: methyl phenyl carbonate=50 g/Kg·Hr, diphenyl carbonate=0.4 g/Kg/Hr) removed from the line 60 was about 2.3 Kg/Hr. The liquid removed to the storage tank 44 contained methyl phenyl carbonate: about 94% by weight. The analysis of the liquid indicated that Ti was detected at 9 ppm. Inspection of the inside of the column revealed white deposits on the wall of the distillation column and the packing.

Example 13 Preparation of the Catalyst

To a reaction flask equipped with a stirrer, a thermometer, a heating and cooling device and a reflux condenser, 3400 g (10 mol) of tetra-n-butoxytitanium and 1700 g of n-butanol were added and the liquid was cooled to a temperature of 0° C. while being mixed well. While maintaining the liquid temperature at 0° C., a mixture of 90 g (5 mol) of water and 2000 g of n-butanol was added slowly for 1 hour. After the addition, the temperature was raised to 80° C. and stirred for 5 hours. The flask was connected to a rotary evaporator equipped with a vacuum controller, vacuum pump and oil bath for heating after cooling down the liquid to room temperature (about 20° C.). The low boiling point components were distilled by reducing the pressure to about 25 KPa while maintaining the liquid temperature at 80° C. When almost all the distillates came out, the temperature was raised slowly to 230° C. and the pressure was reduced further to 1 Pa, and after confirming that there were no distillate, nitrogen was added to return to normal pressure and the temperature was returned to room temperature (about 20° C.) to obtain about 2750 g of pale yellow viscous liquid. This liquid is a catalyst A. The result of element analysis showed that the composition is C, 52.3%, H, 9.9%, O: 20.4%, Ti: 17.4%, and there is one Ti—O—Ti bond since the number of oxygen atoms except for the oxygen derived from BuO was 1 against Ti atom 2. Thus the catalyst A described above is presumed to be a mixture containing butyl titanate dimer [(BuO)₃—Ti—O—Ti (OBu)₃] as a main component.

To this flask, the stirrer, thermometer, heating and cooling device and reflux condenser were reattached and the liquid was heated to 80° C. while being stirred. While keeping the liquid temperature at 80° C., 4700 g (50 mol) of distilled and dehydrated phenol was added slowly. After the addition, the liquid was heated to 180° C. and low boiling point components were evaporated. When there was almost no distillate, the temperature of the liquid was slowly raised to 230° C. to further remove distillates. The flask was connected to the vacuum controller and vacuum pump, the pressure was reduced slowly to 1 Pa and distillates were removed. Then the flask was taken out of the oil bath, cooled to room temperature (about 20° C.) and the inside pressure of the flask was returned to normal by nitrogen. Solid substance of about 4300 g with red orange coloring was obtained. This was the catalyst C. The result of element analysis showed that the composition is C, 64.5%, H, 4.5%, O: 16.7%, Ti: 14.3%. The catalyst C described above is presumed to be a mixture containing phenol adduct of phenyl titanate dimer [(PhO)₃—Ti—O—Ti(OPh)₃.2PhOH] as a main component.

[Production of Aromatic Carbonic Acid Ester]

A mixture consisting of methyl phenyl carbonate (MPC) and the catalyst was continuously supplied as a liquid from an inlet line 62 through a preheater 63 to the location at 1 m from the top of a multi-stage distillation column 61 as shown in FIG. 4, which was composed of a pressure control device 68 and a packed column with 4 m tall and 3 inch internal diameter packed with Dixon packing (6 mmφ) made of stainless steel, and the reaction was carried out by heating with the reboiler (the liquid supply from the inlet line 62: 4.2 Kg/Hr; composition of the liquid supply: MPC=about 99% by weight, catalyst C=12.5 mmol/Kg). The temperature at the bottom of the column was about 195° C., the pressure at the top of the column was about 30 KPa, the reflux ratio was about 2.1. As the result of the reaction, the liquid containing diphenyl carbonate, which was the reaction product, was obtained from the bottom 65 of the continuous multi-stage distillation column through the outlet 70 of the column bottom liquid. The gas distillate from a gas outlet 66 disposed on the top 64 of the column was condensed by a condenser 67. A part of the condensed liquid was refluxed, and the rest was removed from an outlet 69 of the condensed liquid. From this condensed liquid a by-product, dimethyl carbonate, was obtained. From the liquid removed from the line 70, diphenyl carbonate was obtained at a rate of 705 g/Kg/Hr. No deposit or the like were found in the distillation column on inspection.

[Purification of Aromatic Carbonate]

Aromatic carbonate was purified using a device shown in FIG. 2. The device was a continuous multi-stage distillation column which was composed of a column with 2 inch internal diameter and 1 m tall, filled with Dixon packing (6 mmφ). Distillation separation was carried out by feeding the liquid removed from the aforementioned line 60, continuously at a rate of about 100 g/Hr, through a line 25 and a preheater 26, to a continuous multi-stage distillation column 27 at the location about 0.1 m above the middle stage. The heat required for the distillation separation was supplied by circulating the liquid in the lower part of the column through a line 34 and a reboiler 35, and the temperature at the bottom of the multi-stage distillation column was controlled to be about 210° C. The bottom liquid was continuously removed from the bottom of the continuous multi-stage distillation column 27 through the line 34 to a storage tank 36. After removing from the top of the column through the line 28, the distillate was liquefied by a cooler 29 and was removed continuously to a storage tank 33. Distillation separation was carried out by feeding the liquid, which was removed continuously from the storage tank 33, continuously at a rate of about 100 g/Hr, through a line 37 and a preheater 38, to the middle stage of the continuous multi-stage distillation column 39, which was composed of a column with 2 inch internal diameter and 2 m height, filled with Dixon packing (6 mmφ). The heat required for the distillation separation was supplied by circulating the liquid in the lower part of the column through a line 46 and a reboiler 47, and the temperature at the bottom of the multi-stage distillation column was controlled to be about 230° C. The bottom liquid was continuously removed from the bottom of the continuous multi-stage distillation column 39 through the line 46 to a storage tank 48. After being removed from the top of the column through the line 40, the distillate was liquefied by a cooler 41 and was removed continuously to a storage tank 44. To a storage tank 48, white liquid which was solidified at ambient temperature was continuously removed and this was diphenyl carbonate, about 100% by weight. The analysis of the liquid indicated that Ti content was below the detection limit. No deposit or the like were found in the distillation column on inspection.

Comparative Example 3

Aromatic carbonate was purified as in Example 13 except that the catalyst was changed from the catalyst C to phenol adduct of phenoxy titanate [Ti(OPh)₄.2PhOH] (molecular weight without phenol adduct: 420, vapor pressure: about 15 Pa at 230° C.) (the liquid supplied from the inlet line 62: 4.2 Kg/Hr; composition of the liquid supplied: MPC=about 99 wt. %, catalyst C=12.5 mmol/Kg). The temperature at the bottom of the column was about 195° C., the pressure at the top of the column was about 30 KPa, and the reflux ratio was about 2.1. To the storage tank 48, white liquid which was solidified at ambient temperature was continuously removed and this was diphenyl carbonate, about 100% by weight. The analysis of the liquid indicated that Ti was detected at 5 ppm. Inspection of the inside of the column revealed white deposits on the wall of the distillation column and the packing.

Example 14 Polycarbonate was Obtained from Diphenyl Carbonate Produced by the Method for Production in Example 1

Diphenyl carbonate obtained in Example 1: 23.5 g and bisphenol A: 22.8 g were put in a vacuum reactor equipped with a stirrer and polymerized at 8000 Pa for 30 minutes and 4000 Pa for 90 minutes while being purged with nitrogen gas. After this, temperature was raised to 270° C. and polymerization was continued at 70 Pa for 1 hour. Aromatic polycarbonate obtained in such a way was transparent without coloring and good quality. The number average molecular weight was 10,500.

Comparative Example 4 Polycarbonate was Obtained from Diphenyl Carbonate Produced by the Method for Production in Comparative Example 1

Diphenyl carbonate obtained in Example 3: 23.5 g and bisphenol A: 22.8 g were put in a vacuum reactor equipped with a stirrer and polymerized at 8000 Pa for 30 minutes and 4000 Pa for 90 minutes while being purged with nitrogen gas. After this, temperature was raised to 270° C. and polymerization was continued at 70 Pa for 1 hour. Aromatic polycarbonate obtained in such a way had red coloring and the number average molecular weight was 9,800.

INDUSTRIAL APPLICABILITY

According to the present invention, high purity diaryl carbonate can be produced with a catalyst easily removed when producing aromatic carbonate by an transesterification of a starting material and a reactant in the presence of a metal-containing catalyst while distilling off by-product alcohol and/or by-product dialkyl carbonate to the outside of the reaction system. An aromatic polycarbonate produced by transesterification comprising diaryl carbonate produced by the method of the present invention is free from coloring and has high quality.

More preferable methods include a method in which dialkyl carbonate and an aromatic hydroxy compound are continuously supplied to a multi-stage distillation column and continuously reacted in the column while continuously removing produced low boiling point components including alcohol by distillation and extracting generated products containing alkylaryl carbonate from the bottom of the column (Patent Document 55), and a method in which alkylaryl carbonate is continuously supplied to a multi-stage distillation column and continuously reacted in the column while removing produced low boiling point components including dialkyl carbonate by distillation and extracting generated products containing diaryl carbonate from the bottom of the column (Patent Document 56). These methods are the first disclosures of efficient and continuous production of aromatic carbonate. Similar continuous production methods have been thereafter filed, such as a method in which materials are brought into contact in a column type reactor to perform transesterification (Patent Documents 57, 58 and 59), a method in which a plurality of reaction vessels are connected in series (Patent Documents 60 and 61), a method in which a bubble column reactor is used (Patent Document 62) and a method in which a vertical reaction vessel is used (Patent Document 63).

Regarding industrial production of aromatic 

1. A method for producing an aromatic carbonate, which comprises allowing to react a starting material selected from the group consisting of a dialkyl carbonate represented by the following formula (1), an alkylaryl carbonate represented by the following formula (2) and a mixture thereof with a reactant selected from the group consisting of an aromatic monohydroxy compound represented by the following formula (3), an alkylaryl carbonate represented by the following formula (4) and a mixture thereof in the presence of a metal-containing catalyst, with distilling off by-product alcohols and/or by-product dialkyl carbonates to the outside of the reaction system, thereby producing an aromatic carbonate represented by the following formula (5) and/or the following formula (6) corresponding to the starting material and the reactant, wherein the metal-containing catalyst is an organic polytitanoxane composition of a molecular weight of 480 or more which comprises at least two titanium atoms and is dissolved in a liquid phase in the reaction system or present in the form of liquid during the reaction,

(wherein R¹, R² and R³ in the formulas (1) to (4) independently represent an alkyl group having 1 to 10 carbon atoms, an alicyclic group having 3 to 10 carbon atoms or an aralkyl group having 6 to 10 carbon atoms, and Ar¹, Ar² and Ar³ independently represent an aromatic group having 5 to 30 carbon atoms), and

(wherein R and Ar in the formulas (5) and (6) are each selected from R¹, R², R³, Ar¹, Ar² and Ar³ of the corresponding starting material and reactant).
 2. (canceled)
 3. (canceled)
 4. (canceled)
 5. The method according to claim 1, wherein said organic polytitanoxane composition contains at least one alkoxy group and/or aryloxy group as an organic group.
 6. The method according to claim 1, wherein said organic polytitanoxane composition is obtained by a polycondensation reaction of at least one raw material selected from the group consisting of tetraalkoxytitanium, tetrahalotitanium (TiX₄: X being selected from Cl and Br) and titanium hydroxide.
 7. The method according to claim 6, wherein said organic polytitanoxane composition is obtained by sequentially or simultaneously performing two steps of: 1) preparing a partially hydrolyzed product by partially hydrolyzing tetraalkoxytitanium and 2) distilling off a generated low boiling point component including alcohol from the partially hydrolyzed product and subjecting the product to polycondensation.
 8. The method according to claim 6, wherein said organic polytitanoxane composition is obtained by subjecting tetraalkoxytitanium to heating, deetherification and polycondensation.
 9. The method according to claim 6, wherein said organic polytitanoxane composition is obtained by sequentially or simultaneously performing three steps of: 1) preparing a partially hydrolyzed product by partially hydrolyzing tetrahalotitanium, 2) distilling off a low boiling point component from the partially hydrolyzed product and subjecting the product to polycondensation and 3) reacting the resultant with alcohol, removing HX therefrom and alkoxylating the same.
 10. The method according to claim 1 wherein said polytitanoxane composition is used as is or after alkoxy group exchange by reacting the composition with a composition containing at least one member selected from alcohol, an aromatic hydroxy compound and carbonic acid ester.
 11. The method according to claim 1 wherein said titanium containing compound contains at least two Ti atoms in one molecule.
 12. The method according to claim 11, wherein said titanium containing compound contains 2 to 6 Ti atoms in one molecule.
 13. The method according to claim 11, wherein said titanium containing compound contains at least one Ti—O—Ti bond in one molecule.
 14. The method according to claim 1, wherein said metal-containing catalyst has a vapor pressure at 230° C. of 10 Pa or lower.
 15. The method according to claim 1 wherein said metal-containing catalyst is used in a proportion of 0.0001 to 30% by weight based on the total weight of said starting material and said reactant.
 16. The method according to claim 1 wherein said aromatic hydroxy compound is phenol.
 17. (canceled)
 18. (canceled)
 19. The method according to claim 9, wherein said polytitanoxane composition is used as is or after alkoxy group exchange by reacting the composition with a composition containing at least one member selected from alcohol, an aromatic hydroxy compound and carbonic acid ester.
 20. The method according to claim 19, wherein said titanium containing compound contains at least two Ti atoms in one molecule.
 21. The method according to claim 20, wherein said titanium containing compound contains 2 to 6 Ti atoms in one molecule.
 22. The method according to claim 20, wherein said titanium containing compound contains at least one Ti—O—Ti bond in one molecule.
 23. The method according to claim 14, wherein said metal-containing catalyst is used in a proportion of 0.0001 to 30% by weight based on the total weight of said starting material and said reactant.
 24. The method according to claim 23, wherein said aromatic hydroxy compound is phenol. 